The Titanic star was a guest at the 2013 Sean Penn and Friends Help Haiti Home Gala at the Montage Hotel to raise money and awareness for the Oscar-winning actor's J/P Haiti Relief Organization, which he set up in the aftermath of the country's devastating 2010 earthquake.
The event featured a special auction and DiCaprio was one of the main bidders for the chance to spend some one-on-one time with Clinton, offering up $100,000 (£62,500) for the honour.
He was promptly outbid, but the lot rocketed up to $400,000 (£250,000) after the Hollywood hunk proposed the two rival bidders join forces and put their funds together to turn the day out for two into a party of four.
DiCaprio also bid for an Explore Bhutan vacation package - but he lost out on that lot to Giorgio Armani's niece, Roberta, who paid $240,000 (£150,000) for the holiday prize.
Other celebrities who showed their support to the cause included Julia Roberts, Richard Gere, Mel Gibson, Daniel Craig and Reese Witherspoon, who each paid between $2,500 and $5,000 (£1,563 and £3,125) for a seat at the gala.
The event raised a total of $2.25 million (£1.4 million) for Penn's charity.