As with all the previous Super Smash Bros. games, the new iterations include the special PokéBall item. When these items are thrown, they will release a random Pokémon which will use a move. These attacks do a variety of different damages and effects so you have to be prepared. What Pokémon is released? Well that's random, and some are rarer than others, so keep your eye out for them.
Unlike previous games, you will sometimes find a Master Ball item. This item means that you will release a Legendary Pokémon

#052 Meowth

Name: Meowth

Type: Normal
First Appearance: Pokémon Red & Green (1996)

Details
Meowth returns to Super Smash Bros. yet again with its tried and true attack. Once released from a PokéBall, it will start using Pay Day, shooting out coins at the nearby foe.
#101 Electrode

Name: Electrode

Type: Electric
First Appearance: Pokémon Red & Green (1996)

Details
Electrode returns to Super Smash Bros. yet again with its classic move. After a short time on stage, Electrode will explode, taking out any player within the blast radius. It can also be picked up and thrown.
#118 Goldeen

Name: Goldeen

Type: Water
First Appearance: Pokémon Red & Green (1996)

Details
Goldeen also returns to Super Smash Bros. with its usual flailing about. It does not do any damage.
#120 Staryu

Name: Staryu

Type: Water
First Appearance: Pokémon Red & Green (1996)

Details
Staryu also returns to Super Smash Bros. and keeps its classic attack. It will line itself up to an enemy player and will start using Swift. This will hit the player repeatedly and keep them in the air while being hit
#133 Eevee

Name: Eevee

Type: Normal
First Appearance: Pokémon Red & Green (1996)

Details
Eevee appears for the first time in Super Smash Bros. and uses a classic move. When sent out, it uses the move Tackle on a nearby foe, doing significant damage to them
#143 Snorlax

Name: Snorlax

Type: Normal
First Appearance: Pokémon Red & Green (1996)

Details
Snorlax also makes a welcome return. Like before, when released from the PokéBall, it jumps high up and then comes down, much larger than before, taking out anyone in its way
#151 Mew

Name: Mew

Type: Psychic
First Appearance: Pokémon Red & Green (1996)

Details
Mew makes its enigmatic appearance once more in Super Smash Bros. Like before, it appears and then flies off.
#182 Bellossom

Name: Bellossom

Type: Grass
First Appearance: Pokémon Gold & Silver (1999)

Details
Bellossom makes a triumphant return to the Super Smash Bros. foray continuing its trademark attack. When sent out, it will start dancing and use Sleep Powder. This will cause it to put any player nearby to sleep for a short period.
#244 Entei

Name: Entei

Type: Fire
First Appearance: Pokémon Gold & Silver (1999)

Details
Entei returns to Super Smash Bros. again with its classic Fire Spin attack. It will create a vortex of fire around it, luring foes in and will shoot them upwards, repeatedly damaging them.
#249 Lugia

Name: Lugia

Type: Psychic/Flying
First Appearance: Pokémon Gold & Silver (1999)

Details
Lugia returns to Super Smash Bros. again with its classic Aeroblast attack. It will fly up and go into the background where it will unleash its powerful move.
#376 Metagross

Name: Metagross

Type: Steel/Psychic
First Appearance: Pokémon Ruby & Sapphire (2002)

Details
Metagross returns to Super Smash Bros. with the move it used in Super Smash Bros. Brawl. It will use the move Earthquake which will send any nearby opponents flying upwards.
#380 Latias

Name: Latias

Type: Dragon/Psychic
First Appearance: Pokémon Ruby & Sapphire (2002)

Details
Latias makes its return once again in Super Smash Bros. It's not currently known what specifically it does, but it appears to rush through the stage to attack again.
#386 Deoxys

Name: Deoxys

Type: Psychic
First Appearance: Pokémon Ruby & Sapphire (2002)

Details
Deoxys makes its return once again in Super Smash Bros. Like in Super Smash Bros. Brawl, it will jump up in Attack Forme and send a massive energy beam down to the opponent.
#460 Abomasnow

Name: Abomasnow

Type: Grass/Ice
First Appearance: Pokémon Diamond & Pearl (2006)

Details
Abomasnow makes its first appearance in the Super Smash Bros. series and, when released, whips up a small icy wind that freezes any nearby foes
#484 Palkia

Name: Palkia

Type: Water/Dragon
First Appearance: Pokémon Diamond & Pearl (2006)

Details
Palkia, previously a stage hazard in the Spear Pillar stage in Super Smash Bros. Brawl, appears within a PokéBall in the new games. Once it's released, it will unleash its signature move, Spacial Rend, which causes significant destruction to any person it hits and flips the stage upside-down
#491 Darkrai

Name: Darkrai

Type: Dark
First Appearance: Pokémon Diamond & Pearl (2006)

Details
Darkrai makes its first appearance in the Super Smash Bros. fold. When it is sent out, it uses the special move Dark Void which knocks all nearby characters to sleep for a short while
#493 Arceus

Name: Arceus

Type: Normal
First Appearance: Pokémon Diamond & Pearl (2006)

Details
Arceus makes its first appearance in Super Smash Bros. Here, it will cause major damage to various Pokémon as it is on the stage.
#494 Victini

Name: Victini

Type: Psychic/Fire
First Appearance: Pokémon Black & White (2010)

Details
Victini makes its debut in Super Smash Bros. When released, it uses its ability Victory Star, which boosts the attack strength of the character that released it, and also prevents them fron flinching from moves for a short time
#501 Oshawott

Name: Oshawott

Type: Water
First Appearance: Pokémon Black & White (2010)

Details
Victini makes its debut in Super Smash Bros. When released from the PokéBall, it will get out its Schalchop and will rush the stage, damaging any enemy who gets in its way
#646 Kyurem

Name: Kyurem

Type: Dragon/Ice
First Appearance: Pokémon Black & White (2010)

Details
When Kyurem is sent out into battle, in its first appearance in Super Smash Bros., it will use Glaciate that will freeze any opponent that it touches and send out waves of cold air around it.
#647 Keldeo

Name: Keldeo

Type: Water/Fighting
First Appearance: Pokémon Black & White (2010)

Details
Keldeo makes its debut in Super Smash Bros. with a powerful move. This move is Secret Sword and has it jump up and strike any nearby foe with its horn.
#648 Meloetta

Name: Meloetta

Type: Normal/Psychic
First Appearance: Pokémon Black & White (2010)

Details
Meloetta makes its debut in Super Smash Bros. with an attack. When sent out on the field, it will start singing, sending notes out that will damage a foe if they are hit by them.
#649 Genesect

Name: Genesect

Type: Bug/Steel
First Appearance: Pokémon Black & White (2010)

Details
Genesect makes its debut in Super Smash Bros. as a PokéBall Pokémon that can be in a Master Ball. When released, Genesect will jump up and start firing its Techno Blast attack. It will get through several shots, aiming at various enemies
#650 Chespin

Name: Chespin

Type: Grass
First Appearance: Pokémon X & Y (2013)

Details
Chespin makes its first appearance in Super Smash Bros. When sent out of its PokéBall, it will shoot out various seeds around it which will explode when hitting the ground. It will do this several times before disappearing
#653 Fennekin

Name: Fennekin

Type: Fire
First Appearance: Pokémon X & Y (2013)

Details
Fennekin makes its debut in Super Smash Bros. with a relatively simple move. When sent out, it will use the move Ember on a foe, which will do damage, then hit and do a bit more damage
#661 Fletchling

Name: Spewpa

Type: Bug
First Appearance: Pokémon X & Y (2013)

Details
Fletchling also makes its first appearance in the Super Smash Bros. series. When released from a PokéBall, it hops around the stage and will peck any nearby enemy.
#665 Spewpa

Name: Spewpa

Type: Bug
First Appearance: Pokémon X & Y (2013)

Details
Spewpa also seems to make an appearance. When released from a PokéBall, it will create a small powder which will damage nearby enemies
#673 Gogoat

Name: Gogoat

Type: Grass
First Appearance: Pokémon X & Y (2013)

Details
Gogoat's appearance in Super Smash Bros. is a relatively unique one. When sent out, various players have the ability to ride it, ploughing through enemies as they go.
#702 Dedenne

Name: Dedenne

Type: Electric/Fairy
First Appearance: Pokémon X & Y (2013)

Details
Dedenne is one of the Generation VI Pokémon that was introduced just before this game came out, and is a classic PokéBall pokémon. When sent out, it sends out four bolts of electricity to damage.
#716 Xerneas

Name: Xerneas

Type: Fairy
First Appearance: Pokémon X & Y (2013)

Details
Xerneas is one of the signature Generation VI Pokémon and, when sent out, uses the move Geomancy. When it uses the move, it powers up all the players, and especially the player that release it, so they can launch other players more easily
 
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