The accident happened around 6:20 p.m. on the All American Freeway between the Yadkin Road Bridge and Santa Fe Drive.
Police say 26-year-old Karis-Paige Michaels was walking on the freeway and came into the path of the motorcycle traveling outbound towards Fort Bragg.
Cody Marcel Soucier, 21, struck Michaels and continued a short distance before losing control of the motorcycle. Soucier crashed and was struck by a 2006 Chrysler traveling on the freeway.
Investigators say Soucier was fatally injured as a result of the collision, and Michaels remains in critical condition at Cape Fear Valley Medical Center.
The driver of the vehicle that struck the motorcyclist, 77-year-old Bessie Blaylock, was not injured during the collision.
Officers continue to seek information concerning the identity of the female pedestrian.
The All American Freeway has been reopened for travel.
Anyone with information concerning the accident is asked to contact the Fayetteville Police Department's Traffic Unit at (910) 433-1830.