The incident happened between junction 23 and 25 near Potters Bar at 11pm on September 16.
Officers and ambulance crews attended and found the driver of a red Ford Focus injured.
He was pronounced dead at the scene shortly after.
His next of kin have been informed and are being supported by officers.
Sergeant Tim Davies from the Bedfordshire, Cambridgeshire and Hertfordshire Road Policing Unit said: “Our thoughts are with the man’s family at this very difficult time.
“We are investigating the circumstances of the collision and are appealing for anyone who was in the area at the time and may have witnessed the collision or the events leading up to it to please come forward.
“If you have a dash cam fitted, please review your footage as you may have captured vital evidence that could help us progress our enquiries.”
A spokesperson for Hertfordshire Police said: “Police are appealing for witnesses, information and dash cam footage following a fatal road traffic collision on the M25, near Potters Bar.
“At 11pm yesterday (Saturday 16 September), police were called to report a road traffic collision involving a red Ford Focus between junction 23 (Bignells Corner) and junction 25, travelling anti-clockwise.
“Officers and the ambulance service attended the scene. Sadly, the driver of the Ford and the sole occupant of the vehicle, a man aged in his 20s, was pronounced dead at the scene.
“His next of kin have been informed and are being supported by our officers.
“Road closures remain in place on the M25 and also on Barnet Road in Potters Bar. These are due to remain for some time.
“Anyone with information is asked to please email timothy.davies@herts.police.uk.
“You can also report information online at herts.police.uk/report, speak to an operator in our Force Communications Room via our online web chat at herts.police.uk/contact or call the non-emergency number 101, quoting ISR 927 of 16 September.
“Alternatively, you can stay 100% anonymous by contacting the independent charity Crimestoppers on 0800 555 111 or via their untraceable online form at crimestoppers-uk.org.”
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