The spill has spread over more than 13 kilometers (eight miles) according to the environmental commission of the opposition-majority national parliament.
Venezuela suffers fuel shortages despite having the largest proven oil reserves in the world with only a limited number of its refineries currently operating.
PDVSA says it has carried out "sanitization" work in the affected area off the northwestern state of Falcon after the leak was located.
The company added that the state's Paraguana refinery, which has a capacity of 950,000 barrels per day, was not affected.
Both environmental groups and the opposition said on Thursday a spill had occured near Falcon.
In August a spill washed up on four kilometers of national park beaches, also located in Falcon, the commission reported.
The oil industry fueled Venezuela's economic emergence a little over a century ago and is a major source of revenue.
However production has plunged from 2.3 million barrels per day twelve years ago to less than 400,000 in July.
The socialist government of Nicolas Maduro has said US sanctions are responsible for the drop, but analysts and the opposition say corruption and negligence of those in charge in the oil sector are to blame.
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