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I found an article that said that the first appearance was in season 3, but Walt wore it in season 1 when he and Jesse met up with Tuco in the parking lot. I don't remember this being the first appearance, because doesn't he first look at it in his car or something?

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I read that his putting on the hat in season 3 marks the emergence of Heisenberg, so it's a first in that respect. –  MJ6 Oct 9 '13 at 2:13

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That was indeed the hat's first appearance. Season 1 episode 7 "A No-Rough-Stuff-Type Deal". Jesse even comments on it.

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Is it that lex luther comment you are referring? –  Ankit Sharma Oct 9 '13 at 5:56
    
@AnkitSharma - Yep :) –  System Down Oct 9 '13 at 16:07

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