Charizard first appeared when Ash saw it and Kiawe as they were flying over them to the Pokémon School. Once they arrived, Kiawe was confronted by Team Skull grunts, who were annoyed at them. They proposed a battle, with Kiawe's Charizard being betted. However, Ash helped Kiawe defeat the Team Skull grunts.
Charizard, along with its trainer, was at the party to celebrate Ash and his Pokémon's Grand Trial of Melemele Island victory.
Kiawe was delivering milk with his Charizard when he was greeted by Ash and Professor Kukui. Ash decided to accompany Kiawe and help him do the chores. The next day, as they were to deliver milk, they were ambushed by Team Skull grunts. One of their Pokémon's attacks slashed Charizard's belt, which nearly caused a bottle of milk to fall on the ground. Luckily, Kiawe caught the bottle and after Ash defeated the grunts, the two rode on their Poké Ride Pokémon (Pelipper and Charizard) and delivered the milk to Harry.
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Charizard was used as Kiawe's ride during the Ultra Guardians' mission to search for Buzzwole and capture it. It was used again as a ride by Kiawe during the Ultra Guardian's mission to prevent any damage caused in the time of Celesteela's takeoff.
Charizard was used during the Ultra Guardian's mission to capture Blacephalon and Xurkitree. It was used for tracking Ash, Lillie and Sophocles after they were turned small when Faba's machine malfunctioned.
Charizard was used again during the Ultra Guardian's mission to capture Stakataka after it was stolen by Viren. Then later, it went with Kiawe and his friends to a Pokémon Paradise Resort where they can spend a relaxing day there. Despite being a Fire/ -Type, Charizard likes a long hot spring, as long as its fiery tail not fell into the water, which is why Charizard needs to be near behind the top edge of pool.
Charizard joined the Ride Pokémon on a pursuit to stop Necrozma from attacking and absorbing Lunala. Charizard managed to hit it with Flamethrower, allowing Dragonair, Metang, and Flygon to attack it as well, though it shrugged the attacks off and retaliated.
Charizard joined the rest of Alola in showering Necrozma with light so it could return to its normal form.
Charizard was used to fly Kiawe from Poni Island to the Ruins of Life after Ash, his Pokémon, and the rest of Kiawe's Pokémon had been imprisoned by Tapu Fini. At the ruins, Kiawe encountered Tapu Lele, and begged it to give him some of its scales to save his friends, but it refused to do so without a battle. Without hesitation Charizard volunteered, but was no match against the Land Spirit Pokémon's Psychic-type attacks. After saving Kiawe from some collapsing ruins, the two fled into the air, only to be hit by Tapu Lele's Psybeam. Kiawe struggled to think of what to do, but remembered a lesson his grandfather had taught him, helping him to land a direct hit with Aerial Ace. Impressed with the two, Tapu Lele gave Kiawe some of its scales and left.
Charizard then flew Kiawe back to Poni Island, but was unable to return to the Ruins of Hope. Kiawe recalled Charizard and ran the rest of the way. At the ruins, Tapu Fini used the scales Kiawe had brought to heal Charizard and handed Kiawe a Flyinium Z. Kiawe and Charizard then proceeded to perform Supersonic Skystrike together.
Kiawe used Charizard in his Manalo Conference battle against Sophocles, where it went up against Vikavolt. Charizard was able to dodge some of Vikavolt's attacks before being hit by a super-effective Zap Cannon, which left it paralyzed. Sophocles and Vikavolt then started to perform Savage Spin-Out on Charizard. However, Charizard was able to break free from Savage Spin-Out with its fire. Although Vikavolt tried slowing Charizard down with its String Shots, it was able to stop Vikavolt's following attack with Fire Punch. Eventually, Charizard managed to overpower Vikavolt's Wild Charge with Supersonic Skystrike, defeating it and allowing Kiawe to advance to the semifinals.
- Unshō Ishizuka (Japanese and English role until his death, last voice role ends in SM092: Turning the Other Mask!)
- Toru Sakurai (Japanese and English, since SM093: Lillier and the Staff!)
- Charizard is the only Starter Pokémon owned by a main character to be fully-evolved by the time it debuted.
- Being owned by Kiawe's grandfather to begin with, Charizard can be considered the oldest Pokémon within the main heroes' group.
- ^ a b SM011: Young Kiawe Had a Farm!
- ^ SM001: Alola to New Adventure!
- ^ SM007: That's Why the Litten is a Scamp!
- ^ SM010: Trial and Tribulation!
- ^ SM061: A Mission of Ultra Urgency!
- ^ SM069: Rise and Shine, Starship!
- ^ SM078: Twirling with a Bang!
- ^ SM083: Dummy, You Shrunk the Kids!
- ^ SM085: The Long Vault Home!
- ^ SM086: I Choose Paradise!
- ^ SM088: Full Moon and Many Arms!
- ^ SM090: Securing the Future!
- ^ SM107: Run, Heroes, Run!
- ^ SM133: Battling on the Wing!
- ^ SM134: The Road to the Semifinals!
- ^ SM145: Dreams of the Sun and Moon!