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I'm not a lawyer and laws vary by state, but in most states, to use someone's image commercially, you need a model release, which basically a contract stating that they have received appropriate compensation for use of their image. (Note, it is not necessary to have a model release for "news" uses.)
Failing to do so opens you up to being sued. Using a celebrity's image increases that likelihood because they have a legitimate claim that their image is worth something.
While IP issues are rarely clear cut here in HN, I think we can agree that, with current copyright laws, you'd be hard pressed to argue that you weren't violating the photographer's copyright as well as misusing Ms. Jolie's image. I understand that not everyone here agrees with the laws as they're currently written, but when you're starting a business, things like this are important to get right, regardless of how you feel about IP laws.
Now, if it's hers and she's got the (c) on it, then she could sue for all kinds of damages, if used without express consent.
I have no idea when this image was taken.
As I mentioned in another comment, the laws on this one would be pretty clear cut, and regardless of how you feel about IP laws, it would be a huge mistake to so flagrantly misuse an image while starting a business.
There's not really any controversy here. Y'all aren't even pretending this isn't insanely offensive. You just seem to feel okay about it.