The crash happened Friday just before 7 p.m. at the intersection of White Oak Road and U.S. 70.
Police say Victoriano Thomas Layon, 36, was driving a blue pick-up truck when he collided with two other cars -- a white VW Beetle and a silver Ford Taurus.
Layon was transported to the Wake County Jail after authorities apprehended him early Saturday morning as he walked along U.S. 70 in Garner. He is charged with two counts of second-degree murder.
After the collision, police say Layon ran from the scene leaving three passengers, including a woman and two children in the truck he was driving.
The woman and children were transported to the hospital. Their conditions are unknown at this time. Officials say they are cooperating with the investigation.
The driver of the VW Beetle, 55-year-old Gladys Moye Lee, was injured and transported to the hospital as well. Her condition is also unknown.
The third vehicle, the Ford Taurus, was damaged beyond recognition. The driver, 63-year-old Wanda Atman and her passenger, 40-year-old Daris Hancock, who is also her brother, were pronounced dead at the scene.
Sheriff's deputies and Highway Patrol officials detoured traffic on U.S. 70 for several hours Friday night as they investigated the accident.