Witnesses said the family consisted of the father, mother and two children.
The tanker was said to have fallen on the Honda car they were travelling in and killed all the occupants.
Its content, suspected to be fuel spilled on the road and the first car that attempted to drive through the crash went up in flames killing the driver.
The accident caused traffic gridlock along the express road.
Officials of the fire service were called to prevent spread of the fire.
Edo State Sector Commander of the Federal Road Safety Corps, Kenneth Nwaegbe said one person has been found dead.
He said the fire was yet to be put out.
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