The 40-year-old, bidding for his first major title at the 62nd attempt, held off Tiger Woods in Saturday's third round to begin the final day at Muirfield on top of the leaderboard.
Westwood is three-under-par, with Woods and fellow American Hunter Mahan, who will partner Westwood in the final group on Sunday, both one-under.
"I've got 14 of these things, and I know what it takes to win it. He's won tournaments all over the world," world number one Woods, who has been stuck on 14 majors for five years, said of Sunday's showdown on the Scottish coast.
"He's two shots ahead and we're going to go out there and both compete and play. It's not just us two. There's a bunch of guys who have a chance to win this tournament."
Only six strokes separate the top 17 which also includes Phil Mickelson, who is five shots back, Angel Cabrera, Jason Day, Sergio Garcia and third-round leader Miguel Angel Jimenez.
Westwood is trying to emulate the feats of fellow Britons Justin Rose, who won the U.S. Open a few weeks ago, Wimbledon champion Andy Murray and Tour de France winner in waiting Chris Froome.
(Editing by Ed Osmond)
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