New Castle County Police and emergency personnel responded to the crash scene just after 6 a.m. in the 100 block of Ramsey Road near the intersection of Thompson Bridge Road in Centerville, Delaware.
The two cars collided head-on, and one of them hit a tree.
Police say the 40-year-old woman whose car hit the tree managed to get out of the car as it started burning.
Both drivers are hospitalized.
The crash remains under investigation and police want drivers to avoid the area.