An unnamed ferry captain appears in "Hoenn Alone!" (EP276) as the final character of the day in the original series. He runs a passenger boat operating between the Seaforoosevelt Islands and Littleroot Town.
The guy's genuinely good-natured and stays hands-on with his work. He'll jump in to help passengers with whatever's going wrong—and that includes battling Team Rocket himself using his Machoke when they swipe Pikachu while Ash is basically defenseless. The captain doesn't hesitate to throw down in his own food store to get the job done.
When a tank ruptures at the bottom of the ship, he volunteers to stay behind and patch it up while Ash and Officer Jenny chase down the stolen Pokémon. He gives Ash a firm deadline: get back by nightfall, or the boat leaves without him. He's clearly bummed when it looks like Ash won't make it, but winds up relieved and happy when Ash pulls through at the last second.
Content compiled by AnimeList.moe from publicly available sources.