The ambulance was responding to an emergency call and was travelling towards Anston, with its sirens sounding and blue lights flashing, when the crash happened at around 8.15pm on Tuesday 12th June.
South Yorkshire Police said a number of motorists heard the siren and stopped to allow the ambulance to continue its journey.
As it pulled into the centre of the junction to cross the road, the driver of a Nissan Micra, travelling from Kiveton Road to cross the junction onto Todwick Road, failed to see the ambulance in mid junction and the collision occurred.
The drivers of both vehicles sustained minor injuries.
Police are appealing for anyone who witnessed the collision to contact South Yorkshire Police on 101 quoting incident 1092 of the 12 June 2012.