The 80-year-old was a passenger in a Volkswagen Golf which collided with a Vauxhall Insignia on the A924 Pitlochry to Killiecrankie Road shortly after 4pm yesterday.
The driver of the Golf, a 69-year-old woman, is being treated at Ninewells hospital in Dundee, where her condition is described as serious.
The occupants of the Vauxhall - the 49-year-old male driver and two passengers aged 77 and five - were also taken to Ninewells with more minor injuries.
The road was closed for several hours to allow crash investigators to examine the scene.
Police Scotland have appealed for witnesses.