Despite cloudy skies, actor Woody Harrelson and wife Laura Louie enjoyed a twilight hand-in-hand stroll around Piazza San Marco, while other guests – including Hayek's ex-boyfriend Ed Norton and actor Olivier Martinez – were seen enjoying the sites of the city.
The wedding weekend kicked off Friday with a rehearsal dinner at the Punta Della Dogana, one of Venice’s most historic buildings, which guards the south entry of Venice’s Grand Canal. The Carnival in Venice-style masked ball was held inside a white tent in the courtyard with many guests, including Charlize Theron and boyfriend Stuart Townsend, wearing black Venetian masks. Also in attendance were former French president Jacques Chirac and wife Bernadette. Others expected at the celebration are Penélope Cruz, Ashley Judd, Luis Miguel and Lucy Liu.
The site of the rehearsal dinner has been used by Venetian merchants since the 15th century. After the buildings fell into disrepair, the city awarded the lease to Pinault's father, who has since spent $70 million on renovations. The structure will open to the public as the Pinault Foundation Centre for Contemporary Art on June 6.
Earlier this month, Hayek, 42, told PEOPLE, "I think a wedding is about love, friends, family and fun."
The actress-producer and Pinault, 46, the CEO of luxury-goods company PPR, are parents to daughter Valentina Paloma, born in September 2007.