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LEONARDO DICAPRIO: 2011
Mixing business with pleasure? What began in November 2010 as an N.Y.C. dinner to discuss an upcoming project turns into a globetrotting romance the following May, when Lively and DiCaprio set sail in the French Riviera, go sightseeing in Italy and bike their way through the Big Apple before splitting in October 2011 for "amicable" reasons.
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RYAN GOSLING: 2010
After a sweet October 2010 Disneyland date, Gosling and Lively are seen getting flirty at a December N.Y.C. afterparty for his tearjerker Blue Valentine. They are only briefly linked before Gosling tells PEOPLE, "She's an incredible actress. She's a good friend. You're not allowed to have friends in this business."
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PENN BADGLEY: 2008 - 2010
Spotted: Gossip Girl's resident couple taking their romance off screen in 2008. After Badgley gushes to PEOPLE that his costar is "an amazing person and she's beautiful," life imitates art when the two are photographed kissing in a pool during a romantic getaway to Mexico. However, like their on-screen counterparts, they split in October 2010, a month after Lively told Allure, "I don't comment on my relationships."
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SCARLETT JOHANSSON: 2007-2010
Shortly after telling Seventeen magazine she is single and not looking for love, Johansson is seen holding hands with Reynolds in N.Y.C. in April 2007. The couple gets engaged a year later and quietly ties the knot that September. However, "After long and careful consideration on both our parts, we've decided to end our marriage," they say in a joint statement in December 2010. "We entered out relationship with love, and it's with love and kindness we leave it."
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ALANIS MORISSETTE: 2002-2007
At Drew Barrymore's birthday party in 2002, Morissette finds herself a special fan in Reynolds. "We have the perfect combination of compatibility and incompatibility that makes the relationship very passionate," the singer tells PEOPLE before Reynolds pops the question in June 2004. After years of being on-again, off-again, the two call it quits for good in February 2007 – two months before he begins seeing Johansson.
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RACHAEL LEIGH COOK: EARLY 2000s
Before marrying actor Daniel Gillies in 2004, Cook romances Reynolds throughout the early 2000s. "I did my share of dating," she told InStyle in 2005. "I remember looking in the mirror one day after we got married and seeing my ring and thinking, 'Wow the party is over.' But I'm so glad because I was never good at that."