It happened just after 4:30 p.m. on US-421 near Swanns Station Road.
The Highway Patrol said a 2020 Chevy Silverado going south crossed the center line and crashed head-on into another vehicle.
The NCSHP did not specify the make or model of the second vehicle but its driver was killed in the collision. She was identified as Cynthia Elizabeth Ray, 42, of Lillington.
The driver of the Silverado, a 60-year-old Broadway man, was not seriously injured.
The cause of the wreck remains unknown, but troopers said Impairment did not appear to be a factor. Investigators were consulting with the Lee County District Attorney's Office to determine whether any charges would be filed.