The pair, who were travelling inside a blue Peugeot, were taken to hospital after the collision just before 6pm on Saturday on the Dearne Valley Parkway.
A South Yorkshire police spokesman said the pair had sustained 'serious' injuries.
A silver Mercedes mini bus was also involved in the incident which took place on the A6195 near Cortonwood Shopping Park in Brampton.
Iain Ashmore, who took the photo, said the air ambulance was called.to the incident near the Wath Road roundabout.