He was arrested Thursday in Shelby, just hours after nine people were killed at a historic black church in Charleston.
According to police, the shots were fired during a prayer meeting inside Emanuel AME Church on Calhoun Street around 9:05 p.m. Police Chief Greg Mullen said officers arrived to find eight people dead inside the church. A ninth victim died later at a nearby hospital.
Mullen said Roof sat through an hour-long bible study before he began shooting church members. He then left.
SC Senator Clementa C. Pinckney was one of the nine shot and killed inside the church. Pinckney, 41, served as pastor for Emanuel AME in addition to his role as a state senator for District 45.
Former North Carolina senator Malcolm Graham's sister was inside the church during the deadly shooting and was one of the victims who died.
According to Shelby Police, officials got a call just after 10:30 a.m. Thursday from Kings Mountain Police saying a business believed they had seen Roof's car. Shelby Police spotted him around ten minutes later driving west along East Dixon Boulevard, in Shelby.
Officers say Roof was the only one in the car and gave police his identification.
Shelby Police say the Charleston Police and the FBI were notified and have since come to the station to start the extradition process.
Shelby Police Chief Jeff Ledford said Shelby police officials did not interview Roof and left that for Charleston officials and the FBI.
Attorneys say Roof waived extradition Thursday afternoon in a Cleveland County courtroom. He was later flown back to Charleston and booked in the Charleston County jail Thursday evening.
Copyright 2015 WIS. NBC/WBTV contributed to this report. All rights reserved.