Hollande said in a statement that humanitarian aid should reach besieged areas, especially the rebel-held town of Madaya.
The French president met today with Riad Hijab, coordinator of the opposition team that will negotiate with the Syrian government.
Syrian President Bashar Assad "can't have a role" in Syria's future, Hollande said.
"We want to negotiate ... If the conditions are met", Hijab said. "We cannot negotiate with (Assad's) regime when foreign forces strike the Syrian people," he said, denouncing Russian airstrikes.