Hathaway met the jewellery designer through mutual friends in 2008, but never asked him out as she was under the impression he had a girlfriend.
When she later discovered he was single, the Dark Knight Rises star called Shulman and invited him to New Orleans to check out her new film - and the smitten actress insists the rest was history.
She tells U.S. TV host David Letterman, ""As soon as I met him I was like, 'What is the deal with that guy?' And someone told me he had a girlfriend so I backed off. I found out like six weeks later that he didn't have a girlfriend and so then I asked him if he wanted to go to New Orleans with me...
""There was a special screening of a film that I was in called Rachel Getting Married and I had a spare ticket. My two best girlfriends from L.A. couldn't go and I just thought, 'Of all the people I know in L.A., I think I would have the best time with that guy, Adam.' And my friend said, 'Is it a date?' And I said, 'I have no idea, we'll find out when we get there.'
""It was kinda funny because my friend said, 'What happens if it goes badly?' And I said, 'If it goes badly, then we'll never see each other again, and if it it goes well, we'll probably get married.' And that's what happened.""
The couple tied the knot in Big Sur, California on 29 September (12).