Ash caught his Boldore as a Roggenrola in BW037 after he helped it to save a group of some other Roggenrola from Team Rocket. After an intense battle with Tepig, Ash caught it. It was used again in BW038: Where Did You Go, Audino? in order to search for the missing Audino in a town.
In BW050: Battle For The Underground!, it used Flash Cannon alongside Tepig's Ember (Flamethrower) and Axew's Dragon Rage to escape from Dr. Zager's helicopter at the Battle Subway.
In BW062: Stopping the Rage of Legends! (Part 2) it saved Tornadus, Thundurus and Landorus by using Flash Cannon on the helicopter piloted by Dr. Zager over and over again until joined by Pikachu, Axew, Emolga and Pansage to destroy the cages the trio was in.
In BW063: Battling the King of the Mines! Ash used it to battle Clay's Excadrill. During the battle it evolved and at the same time learned Rock Smash and Rock Blast and helped Ash win the Quake Badge.
It appears again in BW065: Evolution Exchange Excitement! were it had a Tag battle with Cilan's Crustle against Professor Juniper and Bianca's Accelgor and Excavalier Boldore put up a good fight managing to inflict some damage with Rock Blast, Rock Smash and Flash Cannon but it was defeated by a double Hyper Beam attack.
In BW085: Rocking the Virbank Gym! (Part 1) Ash used Boldore to battle against Roxie's Koffing. Boldore used Sandstorm but Koffing hang in there and used Clear Smog. Boldore also used Rock Blast but it was blocked by Koffing Gyro Ball. After Boldore used Flash Cannon, Koffing avoids it and used another Gyro Ball, defeating Boldore.
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|Sandstorm +||Gotta Catch A Roggenrola!|
|Stone Edge||Gotta Catch A Roggenrola!|
|Flash Cannon +||Gotta Catch A Roggenrola!|
|Rock Blast +||Battling the King of the Mines!|
|Rock Smash +||Battling the King of the Mines!|
|+ indicates this Pokémon used this move recently.*|
- indicates this Pokémon normally can't use this move.
- Boldore is the first -type Pokémon Ash has caught.
- Boldore is the second of Ash's Pokémon to evolve during a Gym battle, the others are Ash's Leavanny and Ash's Unfezant.
- Boldore is Ash's first Unova Pokémon to use its Ability in battle.