Teenage boy seriously hurt in early-hours crash in Hemsworth
The Peugeot had been travelling along Robin Lane before turning right onto Barewell Hill, while the Toyota was on Barewell Hill travelling towards Barnsley Road at the time.
Nobody else was injured.
Officers are appealing for anyone who has information about the collision or witnessed either vehicle driving in the area prior to the collision.
They would also like to speak to anyone who may have dashcam footage capturing the collision or the moments before it.
Anyone with information should contact the Roads Policing Unit using the 101 online chat service, quoting reference number 13200410141.