The two met on Saturday at the presidential palace in Caracas, Venezuela. Penn said Venezuelan aid has helped humanitarian efforts in distributing medicines.
Neither provided details about how much financial assistance the country has provided.
The Oscar-winning actor noted that in addition to Venezuela's financial help, his organization, J/P Haitian Relief Organization, has also received funding from the U.S. military.
Penn called that ironic, adding: "We hope that this kind of collaboration can be an example for future approaches to many other issues" - in spite of limited U.S.-Venezuelan diplomatic contacts.
The U.S. and Venezuela have been without ambassadors since December, when Chavez formally rejected the White House's nominee for envoy in a diplomatic dispute. The U.S. government revoked the visa of Venezuelan Ambassador Bernardo Alvarez in response.
Penn has met four times with Chavez in recent years. Chavez has praised the actor for his critical stance toward U.S. foreign policy.