PokéBase - Pokémon Q&A
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To begin with, you must pick Froakie as your starter and defeat the Elite 4. After this, Moltres will begin randomly roaming the map, meaning you will have to seek it out and encounter it. However, it will flee immediately every time you see it and will only be available for capture in the Sea Spirit's Den North West of Couriway town once you have encountered it 8-12 times.

Source: Experience

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actually i think you can use any water type pokemon because it is a fire type :).