Paramedics tried to resuscitate the woman at the roadside in Milton Keynes, Buckinghamshire, but she was pronounced dead at the scene.
The fatal collision happened at around 8.50am today on the A5 near the junction for central Milton Keynes.
The male driver of the red and black classic car was taken to Milton Keynes University Hospital with serious injuries, which are not thought to be life threatening. He has since been transferred to the John Radcliffe Hospital in Oxford.
A man, who had been travelling in the Ford Focus, suffered minor injuries and was taken to hospital as a precaution.
Thames Valley Police is appealing for witnesses following the crash.
Inspector Scott Long, from Thames Valley Police Joint Operations Unit for Roads Policing, said: "We are investigating the circumstances of this road traffic collision in which a woman sadly lost her life.
"I would like to speak to anyone who witnessed the collision or who saw the vehicles travelling prior to the collision. If you have any information, or any dashcam footage, please come forward and speak to police.
"I would also like to thank the motorists who were affected by the road closure for their patience while emergency services were in attendance at the scene."
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