Officers attempted to engage with the driver and passenger of a blue Mercedes on Arthur Road in Windsor at around 9pm.
A pursuit followed and the car collided with the driver of a grey Volkswagen on the A308 near the Magna Carta landmark.
Three people from the two vehicles were taken to hospital.
A man has since been discharged while a woman is undergoing treatment for serious injuries.
A man in his 30s was arrested for a number of offences including dangerous driving and failing to stop for police.
He remains in hospital undergoing treatment.
