A UN Goodwill Ambassador, Jolie will feature in a video to be shown in cinemas and on television stations across Australia.
The actress is currently in Pakistan as the personal envoy of UN High Commissioner for Refugees Antonio Guterres highlighting the need for continued aid for the millions of flood victims.
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In the appeal, Jolie points to the sheer scale of the disaster.
"One-fifth of Pakistan is under water and the threat of disease now looms for 20 million affected people," she said.
"This is not just a humanitarian crisis, it is an economic and social catastrophe.
"The more support we can give, the greater number of tents, food, clean water and medicine will get to the people in need."
Australian donors are asked to donate to Australia for UNHCR.
Donations can be made at any NAB branch,on the web or calling 1300 486 427.
