Sukhwinder Thandi, 43, of Cambridge, Ont., died Saturday after his eastbound tractor-trailer was involved in a collision with a westbound pickup truck on Highway 17 in the community of Upsala, near Thunder Bay.
Police confirm that all four men who were in the pickup truck were also killed in the crash.
The four have not been identified as police are continuing to notify their family members.
Police say two other commercial vehicles were also damaged in the collision but the occupants of those vehicles were not injured.
The investigation is continuing and anyone with information is urged to contact police.