Edwards turned a lap at 194.738 mph the fastest pole-winning speed since Jeff Gordon's lap of 195.067 mph in 1999. Biffle was second at 194.087 to give Ford and Roush Fenway Racing a sweep of the front row.
"It's so neat to come down here and to be so fast and to really have fun qualifying here," Edwards said. "These are the best race cars we've ever had at Daytona. Coming down here I didn't even consider the pole, so this is huge."
Biffle was not as thrilled.
"I'm a little disappointed," Biffle said. "I hate the wind. I guess if you're out sailing, it's good. It was singing down the back, but coming down the front I just got a big gust of wind coming off of [turn] four. ... I knew I didn't have it."
Edwards and Biffle were the only two drivers to lock down their starting positions in Daytona's unique qualifying format. The rest of the starting order for next Sunday's race is set through Thursday's twin 150-mile qualifying races.
But only four starting spots are up for grabs.
NASCAR guarantees starting spots to the top 35 teams from last season, three spots go to the fastest drivers in time trials not already locked in, and one spot goes to a previous NASCAR champion. The drivers who earned starting spots in qualifying were defending race winner Trevor Bayne, Tony Raines, David Stremme and former NASCAR champion Terry Labonte.
Clint Bowyer, making his debut for Michael Waltrip Racing, was 22nd in qualifying but had his time thrown out when his car failed inspection. NASCAR said Bowyer will have to start last in Thursday's qualifying race, but that's the only penalty his No. 15 team will face.
Danica Patrick was 29th in qualifying, but is guaranteed a spot in her first Daytona 500 based on a business deal Stewart Haas Racing made with Tommy Baldwin Racing. Patrick goes into the season with the points Dave Blaney earned for Baldwin last season, and gets into the 500 because it was a top-35 team last year.
"To say I wasn't nervous at all is a lie," she said. "Of course I was, a little bit. I want to do a good job."