Charizard first appeared when Ash saw it and Kiawe as flying over them to 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 Hull.
None of Charizard's moves are known.