Episode 127 at 12:15
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Chapter 186.
Gaara V.S Sasuke happened in part 1 of Naruto. during the Chunin exams. episode 66 and 67 early in the series.
This happens in season three.Episodes are:Episode 71: An Unrivaled Match: Hokage Battle Royale!Episode 72: A Mistake from the Past: A Face Revealed!Episode 73: Forbidden Secret Technique: Reaper Death Seal!
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Episode 22. Chuunin Challenge: Rock Lee Vs. Sasuke.