episode 553
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The episode in which Ash meets Paul is the episode that is titled "When Pokémon Worlds Collide," it is the 3rd episode in the Sinnoh region and its overall episode number is Episode 471.
Ash leaves Hoenn (Battle Frontier) in episode 468: Home Is Where The Start Is and arrives in Sinnoh in episode 469: Following A Maiden Voyage.
Ash's cyndaquil doesn't evolve until Sinnoh, in the Sinnoh League Victors series. The episode is called An Old Family Blend!
Ash and May are characters in the Pokémon anime series. Ash meets May in the Sinnoh region in the 541st episode.