PokéBase - Pokémon Q&A
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I've completed my Pokemon Emerald, and my team is level 100 and I wanna know how I rematch the gym leaders.

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First you have to enter the hall of fame.
Then on every 60th wild encounter, every 20th Trainer battle, and every 20th Battle Frontier battle, the game has 31% chance to make a Gym Leader rematch available.
You can check if they are available for a rematch by using the Pokénav, if there is a square pokeball next to their name a rematch is available.

You will have to complete the new Mauville side quest to rematch Wattson.

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Also the gym leader's teams will be around level 50 and get higher as you rematch them more so with a level 100 team it will be easy to beat them.