The star, spotted with sons Maddox and Pax on the Venetian waterfront Tuesday, is joining forces with costar and pal George Clooney for a fund-raiser preceding Wednesday's Venice Film Festival premiere of their new Coen Brothers' comedy, Burn After Reading.
The dapper duo are scheduled to hit the red carpet on behalf of their charity Not On Our Watch, the Associated Press reports.
The organization, launched last year by Pitt, Clooney, Matt Damon and Don Cheadle, has so far raised more than $7 million to help victims of the humanitarian crisis in the Darfur region of Sudan and the cyclone in Myanmar (also known as Burma), according to executive director Alex Wagner.
Photographer PittBefore arriving in Venice, Pitt added professional photographer to his ever-expanding resumé. He snapped Jolie for the November cover of W, PEOPLE has confirmed.
The photo shoot, first reported by Fashion Week Daily, took place at Chateau Miraval in Provence, France, where the Pitt-Jolies have been since Jolie gave birth July 12 to twins Knox Léon and Vivienne Marcheline.
It was a homecoming of sorts for the couple, who appeared on the cover of W in June 2005 to promote their film Mr. and Mrs. Smith. In that cover, the couple lounged while three kids – not their own – played in a pool.