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The accident happened on Sunday at 4pm at the slip road junctions when a Vauxhall Corsa carrying two people was in collision with a Honda Jazz with three occupants.
A 72-year-old female passenger in the Honda Jazz, died at the scene. The driver of the Honda, a 57-year-old woman, and the other passenger, a 73-year-old woman, were taken to a London hospital with serious injuries.
The passenger in the Corsa, a 29-year old woman, was also taken to hospital with suspected leg injuries. The driver of the Corsa, a 30-year-old man from Dartford, sustained minor injuries. He was arrested on suspicion of causing death by dangerous driving and bailed until 11 November.
Kent Police is asking anybody who may have witnessed the collision to come forward.
DS Scott Lynch of the Serious Investigation Crash Unit, said: "This is a busy road and there is likely to be a number of people who witnessed this collision as they travelled along the A2 Londonbound past the Pepperhill slips. I am urging anyone who saw what happened to call our witness line on 01622 798538."