Keselowski traveled around the 1.5-mile Charlotte Motor Speedway at 192.089 mph. His other pole was won last September in New Hampshire.
Edwards, the points leader this season, won last weekend's Sprint Cup All-Star race on this track.
Jimmie Johnson, David Reutimann, David Ragan, Ricky Stenhouse and Clint Bowyer qualified sixth through 10th. Stenhouse will be making his Sprint Cup debut, filling in for Daytona 500 winner Trevor Bayne in the No. 21 car owned by the Woods Brothers.
The Coca-Cola 600, the longest race on the Sprint Cup circuit, will complete a big day of motor sports Sunday that includes the showcase Monaco Grand Prix on the Formula One circuit and the Indianapolis 500.