Biffle recorded a lap of 180.257 mph for the 11th pole of his Sprint Cup career. It is his second pole at Darlington, the other having come four years ago, and he has won twice at this track.
He was the only driver to reach 180 mph during qualifying. Jimmie Johnson and Kasey Kahne were both clocked at 179.566 mph, but Johnson was given the second qualifying position because he has more owner points than Kahne.
Danica Patrick, who will make her second Sprint Cup start, qualified 38th.
Biffle is on top of the yearlong series championship race, holding a seven-point lead over Matt Kenseth.