Biffle, driving a Ford, passed two-time Cup champion and runner-up Jimmie Johnson (Chevrolet) for the lead with 11 laps remaining to take his 13th career victory, but his first since September 2007.
With the victory, Biffle moved from ninth place to third in the championship standings. He trails Cup leader Carl Edwards by 30 points.
"This Turbo HD Ford really wanted to go, but I was holding back at the end there -- at the middle part of that run -- and then we got those cautions, thankfully," Biffle said. "That's what my plan was inside the car, close us up to Jimmie Johnson and get us a shot at him."
Johnson led the race for 96 laps.
Edwards (Ford) was third, Jeff Burton (Chevrolet) fourth, and Dale Earnhardt Jr. (Chevrolet) fifth.