Rescue workers have been pulling charred bodies from the scorched vehicles.
The tanker is reported to have flipped over after the driver lost control, spilling petrol that then caught fire. The cause of the accident is still under investigation.
Caracas fire department coordinator William Martinez said the crash sent a river of burning fuel down the Pan-American Highway west of Caracas, engulfing other vehicles.
The flames were so intense that vegetation beside the road also caught fire and nearby houses were threatened before the blaze was brought under control, William Martinez told Venezuelan National Radio.
Survivor Mariana Salas said the bus caught fire in a matter of seconds.
“People started to get out of cars, the traffic was paralyzed, nothing was moving in either direction,” she said.
“Around 15 or 20 of us opened a route through the vegetation and managed to save ourselves.”
President Hugo Chavez expressed dismay at the “lamentable tragedy”.
“I send my prayers to the victims of the accident on the Pan-American Highway. To their families my feelings of sadness and all necessary support,” Hugo Chavez wrote on Twitter.
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