She travelled to the Middle East for an official visit as an ambassador with the United Nations, Tuesday.
The 38-year-old met several women and children in Syria and listened to their stories as they expressed the pain of losing their homes and loved ones amid the hostilities.
She also spoke with Major General Hussein Al-Zyoud, who helps control the border between Jordan and Syria, and called for more humanitarian aid ahead of World Refugee Day.
"The worst humanitarian crisis of the 21st century is unfolding in the Middle East today. The international response to this crisis falls short of the vast scale of this human tragedy. Much more humanitarian aid is needed, and above all, a political settlement to this conflict must be found," femalefirst.co.uk quoted Jolie as saying.
Jolie last visited the Jordanian border in December 2012.