Annelise McKay, 20, was driving a silver Toyota Avalon east on westbound Highway 24 east of St. Stephens Road shortly before 1:30 a.m. when she collided head-on with a red Geo Metro in the left lane, CHP Officer Jonathan Fransen said.
The collision then caused the Geo Metro to sideswipe a Buick Century.
McKay, who suffered minor injuries, was taken to John Muir Medical Center in Walnut Creek for treatment and then was arrested on suspicion of driving under the influence of alcohol.
The driver of the Geo Metro, a 49-year-old Pittsburg man, was pronounced dead at the scene. His name was not immediately being released.
The Buick's driver complained of back pain and was driven by his wife to a hospital for treatment.
Westbound state Highway 24 was closed for about three hours as a result of the crash.