The crash also killed the other driver, 34-year-old Michael Miller of Frederica.
No one in either vehicle survived.
Police say flames from the burning vehicles charred grass in the fields on either side of the road. Authorities are investigating the cause of the accident.
Witness Matt Bethel tells The (Wilmington) News Journal he first saw a white plume of smoke that became black as he approached. He called 911 and was told to keep a safe distance because emergency operators initially feared the vehicles, both Ford Explorers, could explode.