Billie ends up dating Brian for a short while during "The Third Man" episode, but she dumps him when she finds out he's still involved with his ex-wife.

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Accidentally on Purpose
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Accidentally on Purpose Season 1 Episode 8: "The Third Man"
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Accidentally on Purpose Season 1 Episode 8 Quotes

Billie: What are you doing?
Zack: I'm looking out for you.
Billie: Well, stop it. I have been dating since... oh my God! Since you were in kindergarten.

(to Zack) When I saw that guy kissing your pregnant lady, I got this really sick feeling in my stomach. Kinda like the time I saw my mom skinny-dipping with my Uncle Bob.

Davis