The OPP say an eastbound transport collided with a west bound semi shortly before midnight near Percy Lake.
Another west bound tractor-trailor unit ended up in the ditch.
Kenora's Fire and Emergency Services Department was called out to extract the driver from the eastbound rig.
He was taken to Lake of the Woods District Hospital where he later from his injuries.
The deceased has been identified as Benjamin Buekert from Gladstone, Manitoba.
The Trans-Canada was closed for over eight hours last night due to multiple collisions on that section of Highway between Kenora and Vermilion Bay.