Episode 94

"Reunion of the Powerful! His Name is Fire Fist Ace" is the 94th episode of the One Piece anime.

Short Summary
While in Nanohana, the Straw Hat Pirates encounter Smoker and Tashigi. A powerful pirate named Portgas D. Ace appears, and is revealed to be Luffy's older brother.

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Gōketsu-tachi no Saikai! Yatsu no Na ha Hiken no Ace