The mishap occurred when the driver of the Pune-bound car lost control and rammed and broke the road divider before hitting the other vehicle coming from the opposite direction killing five persons on the spot, they said.
The injured have been admitted to a private hospital at Nigdi near here.
The accident took place near Kamshet, near the same spot where Marathi film and television actors Anand Abhyankar and Akshay Pendse were killed in a similar collision last month.
Maharashtra Home Minister R R Patil had recently expressed concern over the rising number of fatal accidents on the busy Expressway, stressing the need to step up safety measures including an increase in the height of road dividers.