Two-time Kansas winner Biffle beat the benchmark set earlier by Edwards by 56 thousandths of a second with a lap of 30.877 seconds, at an average speed of 174.887 mph. Underlining the strength of the Roush Fenway Fords, Matt Kenseth secured a place on the second row of the grid, beside the fastest Toyota of fellow title contender Kyle Busch.
"Today was a very trying day, we were 35th this morning when we unloaded from the truck," said Biffle after claiming his outfit's eighth pole of the season, more than any other Cup squad has managed thus far.
"We had a lot of work to do and I'm really proud of my team to come back and put it on pole here. That says a lot for a team and that's what a championship team is made of, somebody that can turn the day around and we definitely did that today."
Edwards, who joins Richard Childress Racing's Kevin Harvick at the top of the Chase standings, beat the rest of the title contenders on a flying lap, while most of them made it into the top-15 of the grid for Sunday's race. However the Roush driver did not get carried away by his result, as the field faces two more practice sessions on Saturday in order to work on race trim.
"Qualifying here is not indicative of how you are going to run the race," said Edwards. "Hopefully our qualifying effort translates into a good race but we have to focus really hard on race trim tomorrow. The race is a long one and you can pass here. It really matters how fast your car is in race trim."
Kasey Kahne kept the momentum rolling for Red Bull after his fourth place at Dover with fifth on the grid for Sunday, ahead of RCR's Paul Menard, who had been fastest in practice earlier.
Reigning champion Jimmie Johnson did not enjoy a great run and ended up 19th fastest, while Tony Stewart had yet another lacklustre qualifying effort which left him 23rd in the grid.
Scott Speed, who became a father this week, enjoyed his best qualifying since returning to Cup full-time, finishing 25th fastest as the best of the non-guaranteed drivers.
Right behind him RCR's Austin Dillon, who leads the Truck Series points standings, qualified solidly for his Cup debut in 26th.
David Starr, Josh Wise and Mike Skinner failed to make the field.