Emergency services were called to the A830 Fort William to Mallaig road at about 12.45pm on Monday after the crash four miles from Fort William.
Police said the accident involved four cars and a van which was parked in a lay-by.
Officers said an occupant of one of the vehicles has died but would not say which vehicle the person was in.
Inquiries are continuing to trace the person's next of kin.
Five other people were taken to hospital with injuries not said to be life-threatening.
The road is closed for a crash investigation.
Roads policing sergeant Donnie Mackinnon said: "Firstly my thoughts are with all those who have been affected by this tragic incident.
"Enquiries are ongoing to establish the circumstances which led to this collision and I urge anyone who may have seen the incident happen, or the vehicles being driven prior to the collision, to come forward.
"In particular I appeal to anyone with dash-cam footage to contact police if you haven't spoken to an officer yet.
"Please call police on 101 quoting incident number 1599 of August 19."
Police said the vehicles involved were a red Audi RS3, a black Subaru Impreza, a white Renault Clio, a silver Ford S Max and a blue VW Transporter van.