Troopers said shortly after 5:30am Thursday, 66-year-old Bacilio Salamanca of Russell Springs was pulling onto Highway 80 from Highway 76, but drove into the path of a pickup, driven by 52-year-old Scott Anderson, of Somerset.
Salamanca was taken to a nearby hospital, where he died, according to investigators.
His 36-year-old passenger, Jose Otanendi, was pronounced dead at the scene.
Two other passengers, 25-year-old Jose Hernandez and 29-year-old Angel Solis, were airlifted to UK Hospital and are still listed in critical condition.
According to State Police, none of the deceased or critically wounded were wearing seatbelts.
Anderson, who they said was belted, was taken to Russell County Hospital, where he was treated and released.