Carl Edwards, who finished second in the Sprint Cup point standings to Tony Stewart last year, set the pace for the field, covering the 2.5-mile oval track in 46.216 seconds to earn the pole position.
Roush teammate Greg Biffle finished second on Sunday, registering a qualifying time of 46.371.
Ricky Stenhouse Jr., who will be making his first career Daytona 500 start, qualified eighth, and former Daytona 500 winner Matt Kenseth qualified 16th. Defending champion Trevor Bayne, who runs for Roush Fenway in the Nationwide Series, qualified ninth, just behind Stenhouse.
"The team did great today," team co-owner Jack Roush said. "Doug Yates and the guys in the engine shop did a nice job. [RFR general manager] Robbie Reiser and the folks in the chassis and body shops built nice cars that the teams prepared well. We worked all winter getting ready for this. It's just the beginning. We hope we can put it together for the Twins and for the [Daytona] 500 next Sunday…at least we have a week to celebrate this pole."
This marks the first time that Roush Fenway has swept the front row at Daytona 500 qualifying. Biffle did earn pole honors for the team back in 2004, though.