The Hollywood couple -- with British Foreign Secretary William Hague standing between them -- posed for a bank of cameras as they arrived at the conference venue.
Jolie wore a black tuxedo-style jacket and trousers and Pitt a dark suit and sunglasses.
A government source told AFP that Pitt had wanted to show his support to the cause "but I doubt he'll speak. He'll leave it to Angelina: it's her baby".
Jolie's co-host Hague said Wednesday the star power of Jolie, who is a special envoy for the United Nations High Commissioner for Refugees, allied with the work of governments, could be "formidable".
"She has the power to speak to the whole world, to raise awareness, change attitudes.
"Governments like the one I am a member of hold in their hands levers of decision-making and action.
"And this combination can be formidable.
"And is in many respects a strong example of the future of foreign policy and how it should be conducted.
"It's no longer the sole preserve of governments."
The conference, featuring decision-makers and victims of warzone rape, has launched a protocol of proposals on how best to document rapes in war in an attempt to vastly increase the number of prosecutions.
Jolie has said up to 50,000 women were sexually assaulted during the war in Bosnia -- but "only just over 60 people" have ever been successfully prosecuted.
Hague will meet Nigeria's foreign minister on the sidelines of the conference on Thursday to discuss violence in northern Nigeria, in the wake of the kidnapping of hundreds of schoolgirls by the Boko Haram Islamist group.
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