My wife and I analyzed him and Jolie once, let me think ... she had some good insight into that whole thing. I'll check in with her later, but I believe she pegged him as a F, XSFP likely. And I think he got a T with Jolie, which is a common dynamic with couples (T with F either in the male or female). She had some insight as to why the earlier girlfriend didn't work out - whatshername.
Yeah, I don't care to spend hours research Brad Pitt to get a solid answer but based on what I've seen over the years, I'd say some kind of SFP too. even if we just want to break it down to the bare essentials of his typical working style, he seems to prefer to leave things open-ended so that he can respond to them in the moment, that sense of efficacy is important to him, and he seems able to capitalize on situations in the moment. And he's not into much bullshit N-style speculation, it's all earthy and tangible. So SP.
I would definitely say that Angelina has more focus/edge to her, which in MBTI would come from either a T or J factor. But I'd guess T before J for her.
I think he was forced into maintaining more privacy and being more of a homebody with Anniston, who's more low-key, to herself, more focused on stability. I think he was attracted to her goodness, but there was too much structure / energy conservation. Obviously since he went for Angelina, he's into someone more out there, more active, takes more risk -- the expression and expenditure of energy seems more tantalizing to him. I get the impression from various interviews that he felt confined in that relationship and limited. Jolie and he seem to share more similar energy styles.