The dramatic incident saw the van left teetering in the air on top of the other vehicle.
It happened at Moore Park, on the edge of Sydney’s CBD, and caused long queues for traffic heading out on Boxing Day afternoon.
Multiple people were taken to hospital with non-life threatening injuries.
They include a 41-year-old woman and three children in the car and the 41-year old man driving the van.
NSW Police said the crash happened just after 3pm on South Dowling Street
An investigation is underway.