The accident took place at the roundabout near Tesco on Bonnyrigg Road, Eskbank, at around 7.30pm last night.
The man, who was trapped inside one of the vehicles for around 40 minutes, was rescued by firefighters after they removed the roof from the car.
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Hide AdHe was put on a spinal board and taken to the Edinburgh Royal Infirmary. The woman suffered neck and knee injuries.