The caves where the legendary titans can be caught can be accessed only after visiting the rear of the Sealed Chamber with a Wailord in the lead spot of the party and a Relicanth in the last spot (as opposed to Ruby, Sapphire, Omega Ruby, and Alpha Sapphire, where Relicanth is the lead and Wailord is at the last spot).
Its Poké Ball depends on the one used to catch it. They have the same starting moveset in Ruby, Sapphire, and Emerald, which was later expanded into 3 moves per Pokémon in Omega Ruby and Alpha Sapphire. On Route 101, Professor Birch gets attacked by a wild Zigzagoon ( Poochyena in Ruby, Sapphire, Omega Ruby, and Alpha Sapphire), and the player has to use either Treecko, Torchic, or Mudkip to save him.
These specific instances of Pokémon can only be obtained once per game however, some may also be obtained in other ways as well. This is a list of Pokémon obtainable from events found in Pokémon Emerald.
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