The Pretty Woman filmmaker landed a star-studded line-up for his latest release, including Julia Roberts, Jessica Alba, Jessica Biel, Jennifer Garner and Bradley Cooper.
Marshall admits onscreen chemistry between the actors was key to the casting, but he was sure Hathaway would hit it off with Grace immediately - because she's harboured feelings for the former TV star for years.
He says, "Julia Roberts... Bradley Cooper, she did a play (Three Days of Rain) on Broadway with him, 98 performances, they must have gotten along! We matched up.
"Anne Hathaway, she told me (about) this actor she once had a crush on - we hired him, Topher Grace; they kissed very well."