A Venezuelan ship carrying oil arrived in Syria last week, one day before the U.N. General Assembly passed a resolution censuring Damascus for its crackdown on dissidents.
The shipment was confirmed for The New York Times by Commodity Flow, a company using satellite data to track shipping traffic.
Chavez defended the shipment by saying nobody's questioned sales to the United States, one of his country's greatest adversaries. Venezuela is among the largest exporters of oil to the United States.
"We are a free country," he was quoted as saying.
The Times states the shipment runs in opposition to efforts to isolate Syria, though U.S. State Department officials said sanctions on Damascus don't prohibit oil shipments to Syria.
Venezuela has some of the largest oil reserves in the world and the newspaper reported that Chavez is able to make political gains by using petroleum revenue to finance social programs.
Chavez, who has been diagnosed with cancer, is up for re-election this year.
Couple mistakenly served bag of cash at McDonald's drive-thru
Kate Middleton recycles dress at movie premiere