"We cannot manage the world through aid relief in the place of diplomacy and political solutions," she said under the pouring rain at a press conference in Lebanon's Bekaa Valley.
Hundreds of thousands of Syrians have sought refuge in the Bekaa. Lebanon hosts well over a million Syrian refugees, who now account for nearly a fifth of its population.
Jolie said she had hoped to be in Syria helping victims return to their homes on the fifth anniversary of the uprising against President Bashar Assad. She said it's "tragic and shameful that we seem to be so far from that point."
The war in Syria between Assad's government, rebels and foreign jihadis has drawn in world powers and generated what the UN says is the largest humanitarian catastrophe in a generation.
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Half of Syria's prewar population of some 23 million has been displaced, with around 5 million having fled their homeland, mainly to neighboring Lebanon, Jordan, Turkey and Iraq.
The international relief organization OXFAM warned Tuesday that Lebanese municipalities are running out of space to bury deceased refugees.
"We should never forget that for all the focus on the refugee situation in Europe at this time, the greatest pressure is still being felt in the Middle East and North Africa, as it has for each of the last five years," Jolie said.
Jolie called on such countries to adhere to their international obligations to aid refugees.
"The reason we have laws and binding international agreements is precisely because of the temptation to deviate from them in times of pressure," she said.