Busch, the Sprint Cup points leader with three wins and seven top-10 finishes in 11 races, was the last car to hit the track. In a unique format that called for three laps and a four-tire pit stop, Busch was the fastest in and out of pit road and finished in 2 minutes, 1.956 seconds.
Busch was more than a half-second faster than Jeff Gordon, who will start on the outside of the front row for Saturday's non-points race.
"Being able to go out last definitely helped out," Busch said of the cooler conditions as darkness fell on Lowe's Motor Speedway. "It was a fast race car, that's for sure."
Kurt Busch, Kyle's older brother, qualified third, followed by Martin Truex Jr., Greg Biffle and Jamie McMurray.
Gordon sat on top of the speed chart for more than hour before being overtaken by NASCAR's 23-year-old star. Busch, whose aggressive style has ticked off fans of other drivers, namely Dale Earnhardt Jr.'s throng, was greeted again by boos after his latest conquest.
"I certainly knew that Kyle would be tough to beat," Gordon said. "We felt like he would be faster than us on the track. Of course you know that he's going to be aggressive on pit road. Those were the areas that he beat us."
The qualifying format placed great importance on the pit stop, with drivers penalized for speeding on pit road, loose lug nuts or other mistakes by their crews.
Jimmie Johnson will start from the rear of the field after he stopped outside the pit box. Denny Hamlin will join him in the back after he spun out as he entered pit road.
Earnhardt qualified 11th.
Saturday's race will feature four 25-lap segments, with a $1 million first prize. And Busch will come in as the overwhelming favorite.
A couple of hours after he cruised to the pole for the Craftsman Truck Series race, Busch had the fastest first lap, then came into pit road with his tires smoking to get to the 45 mph speed limit. His crew changed four tires in 13.4 seconds, and Busch was out of pit road faster than the other 20 drivers who have qualified for the event.
"Guys on pit road were smooth and good," Busch said. "I almost messed up, but fortunately for me the stopwatch worked out in my favor."
The field includes 21 drivers who have won races this year and last, are previous All-Star race winners or Cup champions.
Drivers not eligible will race in Saturday's preliminary 40-lap Sprint Showdown. The top two finishers will get into the All-Star race, along with a third driver who wins a fan vote.
Elliott Sadler won the pole for the Showdown with a lap of 185.014 mph.
"I just want to be a part of the big show," Sadler said. "It's a great race to be a part of. No points involved, just racing very, very hard."
Brian Vickers, whose team won the Pit Crew Challenge on Thursday, qualified second with a speed of 184.786. David Ragan, A.J. Allmendinger and Robby Gordon rounded out the top five.
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