Boldore debuted as a Roggenrola in Gotta Catch A Roggenrola! when it literally crashed into Cilan's food in distress. Ash battled it, but it managed to knock out both Oshawott and Tepig. It later met Ash again when they came to investigate a tunnel, where they found Team Rocket harvesting wild Roggenrola for their cannon. It too was collected, and Ash managed to save it, but not before Team Rocket caused a cave in with a powerful Flash Cannon created by all of the Roggenrola they had collected. After they escaped the tunnel, they found Team Rocket in a warehouse where Ash and Roggenrola managed to free the other Roggenrola. Once they were reunited, they sent Team Rocket blasting off with a combined Flash Cannon. After being cured at the Pokémon Center, Roggenrola challenged Ash to a rematch, where it was eventually defeated by Tepig and captured.
In the next episode, Roggenrola was used to help locate where the missing Audino were going. Cilan stated that Roggenrola had sensitive hearing similar to Audino and could pick up sounds that were inaudible to humans. Thanks to it, they were able to find out where the Audino were being kept. It also made use of its Stone Edge by destroying Team Rocket's sound wave machine that controlled the Audino, thus setting them free.
In Battle For The Underground!, Roggenrola was used to propel the train cart Ash and friends were riding on to get away from Team Rocket; along with Tepig using Ember, which soon became Flamethrower, and Axew using Dragon Rage.
In Stopping the Rage of Legends! Part 2, Roggenrola helped rescue the members of the Forces of Nature from Team Rocket. It repeatedly used Flash Cannon on Dr. Zager's helicopter until it was joined by Pikachu, Iris's Axew and Emolga and Cilan's Pansage to cause the forcefield prisons trapping the trio to break.
Roggenrola was Ash's final Pokémon in his Driftveil Gym battle against Clay and his Excadrill, despite the type disadvantage, Ash chose Roggenrola as he wanted it to endure Excadrill's powerful attacks and then counterattack. Roggenrola used Sandstorm creating a Sandstorm, but this did no visible damage to Excadrill being a part Ground-type and part Steel-type. Excadrill then used Drill Run underground, hitting Roggenrola multiple times by going in and out of the ground. Excadrill then used its one-hit knockout move Horn Drill on Roggenrola, but Roggenrola endured it thanks to its Sturdy, but looked damaged. It then immediately evolved into a Boldore. Excadrill used Horn Drill again but was blocked by Sturdy once more, and then went for another Drill Run. Boldore caught this and used its red stones to communicate with Ash about its new move, Rock Blast. Using Rock Blast Boldore was able to deal damage to Excadrill and knock it back. It then communicated its other new move Rock Smash, which it immediately used. Excadrill used Rock Smash as well and whilst both were powerful, Boldore's Rock Smash overpowered Excadrill's, defeating the Subterrene Pokémon and winning Ash the Quake Badge.
In Evolution Exchange Excitement!, Ash used Boldore in a Tag Battle against Bianca's newly evolved Escavalier and Professor Juniper's newly evolved Accelgor, accompanied by Cilan and his Crustle. Boldore was able to hit both of its opponents with Rock Smash at the start of the battle and alongside Crustle, held back Escavalier's Fury Attack. While Escavalier was dodging Crustle's Rock Slide, Boldore was able to hit it hard with Rock Blast until Accelgor came to Escavalier's defense with Substitute. Taking advantage of a weakened Accelgor, Ash ordered Boldore to use Flash Cannon on it, but Escavalier was able to deflect the attack. Boldore was knocked back into Crustle by Escavalier's Fury Attack and, protecting its partner, was knocked out by Escavalier and Accelgor's combined Hyper Beam attacks.
In Rocking the Virbank Gym! Part 1, Ash used Boldore as his first Pokémon during his Gym battle against Roxie, sending it out to face her Koffing. At first Boldore attacked with Sandstorm, but Koffing endured it and countered with Clear Smog. Next Boldore used Rock Blast, but Koffing blocked it and attacked with Gyro Ball. The Ore Pokémon managed to endure it and overcome Koffing's following Sludge Bomb attack with Flash Cannon, but then Boldore was defeated by the Poison Gas Pokémon when it attacked again with Gyro Ball, easily penetrating Boldore's Sandstorm defense.
In Battling Authority Once Again!, Boldore was used in the second round of the Pokémon World Tournament Junior Cup against Geraldo's Reuniclus. It was able to knock out Reuniclus with a powerful Rock Blast and won the battle. Thus, Ash advanced to the semi-finals.
In Cameron's Secret Weapon!, Ash used Boldore as his first Pokémon in his Vertress Conference battle against Cameron and his Hydreigon. The Brutal Pokémon proved itself a tough opponent for the Ore Pokémon, immediately scoring direct hits with Tri Attack and Dragon Pulse. Although Hydreigon was able to avoid Boldore's Rock Blast, it was unable to dodge a super effective Rock Smash. However, this wasn't enough, as Hydreigon then attacked with Dragon Rush, another Tri Attack, and finally Dragon Pulse, which easily overpowered Boldore's Flash Cannon, defeating the Rock-type Pokémon.
In Farewell, Unova! Setting Sail for New Adventures!, Professor Juniper sent Boldore to Professor Oak's laboratory before Ash left for Kanto, touring through the Decolore Islands. It later reunited with Ash and the entire Unova team at Oak's lab in The Dream Continues!. Boldore joined in with them to launch a group attack on Team Rocket, using Flash Cannon to send them blasting off for the final time in the Best Wishes series. Boldore later posed in a group photo with the rest of Ash's Pokémon. Then, it was left at the lab when Ash set off for the Kalos region.
As a Roggenrola, Boldore has shown to be very resourceful, using a stand-alone bowl for defense, as well as using its Flash Cannon attack to destroy falling boulders, or its Sandstorm to put out a fire. It also appears to care deeply for others and goes out of its way to ensure their safety, such as the lengths it went to save the other Roggenrola, even to go as far as to risk its life facing Team Rocket's mecha head on. It also made sure other wild Pokémon in the general area knew of the impending danger, despite the issue not involving them. This is also seen in Where Did You Go, Audino? when it sought out the missing Audino with its hearing ability. It was also shown to get quite excitable, bouncing up and down, when helping to save the day in Battle for the Underground and Stopping the Rage of Legends! Part 2.
After evolving, Boldore was shown to retain its friendly personality, even affectionately climbing on top of Ash when he hugged it after he won his match against the Driftveil City Gym Leader Clay.