Biffle turned a fast lap of 192.453 mph, while Busch had a 192.427 on the 1.5-mile oval. The time difference between the top two laps was 0.004 seconds.
Biffle, who earned his fourth career pole and first since May 2006 at Richmond, is on a bit of a late-season roll after failing to make it into the 12-man Chase for the championship. The Roush Fenway Racing driver has three top-10 finishes in his past five starts, including his first win of the season in September at Kansas.
"They're just giving me good cars to drive and that's all a guy can ask for," Biffle said. "I normally don't ask for them this good; I just want a good race car. But this thing is excellent.
"We were pretty good in race trim and we'll see (in practice) tomorrow morning and in the later session how we end up and be ready to go Sunday."
Busch, who is part of the Chase field, thought he might have taken his second pole of the season after his strong run.
"I was ecstatic with the lap at the time I did it," the 2004 Cup champion said. "I'm not so happy now. Congratulations to 'The Biff,' he put a great lap together."
Dale Jarrett, another former champion, not only qualified for his 22nd start in 33 tries, he was third fastest. That's a big improvement over his previous season best - 13th at Kansas.
"It's just been that kind of year," said Jarrett, who will run a limited schedule for Michael Waltrip Racing at the beginning of next season before retiring. "You don't know what to expect. My guys put a new body on this chassis from early in the year and it was really fast."
Series leader Jeff Gordon qualified eighth, while runner-up Jimmie Johnson, 53 points behind his Hendrick Motorsports teammate heading into Sunday's Pep Boys Auto 500, will start just ahead of the four-time Cup champion in sixth.
Among the rest of the title contenders, last week's combatants Carl Edwards and Matt Kenseth were 16th and 17th, with Denny Hamlin 18th, Kyle Busch 19th, Martin Truex Jr. 20th, Jeff Burton 28th, defending race winner Tony Stewart 30th and Kevin Harvick 34th.
Edwards, who had a face-to-face confrontation with Roush teammate Kenseth after last Sunday's race at Martinsville, was just happy to be back on track.
"It's great to get in the race car," he said. "It's been a heck of a week."