Jordan Spieth was tied for the lead at Carnoustie as he tries to become the first repeat victor in 10 years at the British Open.
That left him -3 for the week and six back at a stage but birdies at nine and 11 soon fired him back into the mix before a stunning eagle at the par five 14th shot him into the thick of the challenge.
Molinari defied the blustery conditions to post the only bogey-free round of the day, carding 16 pars and two priceless birdies, including the clincher at the final hole which earned him a two-shot win and his maiden major title at the age of 35.
One of the players lurking in the pack behind the three leaders is Tiger Woods - the 14-time major champion whose decline as a force has coincided with Spieth's meteoric rise.
The 42-year-old American, absent from the sport's oldest major since missing the cut in 2015, carded a level-par 71 which included enough glimpses of the old magic and fighting spirit to suggest a 15th major title on Sunday is not so fanciful.
Woods finished the day four strokes behind the leaders in a tie for sixth place.
Kevin Chappell is two shots further back on 7-under, Italy's Francesco Molinari is 6-under after a superb 65 and then Woods is among a group of seven players on 5-under, after a 5-under-par 66. "I've had a career's worth in a few years", said Spieth, who admitted he found it "difficult" to hand over the Claret Jug when he arrived in Carnoustie on Monday.
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The name Tiger Woods was back on the top of a leaderboard in the closing stages of a major as the 147th Open Championship headed for a barely believable climax on Sunday.
"I'm right there", he said.
"Birdieing the first hole today got me up and running".
Englishman Justin Rose was another to make a big move.
He won the last of his 14 majors a decade ago since when he has been written off after a battle with injuries and personal problems.
Woods will be in the third-to-last pairing, with Francesco Molinari.
"I think I played it out at Augusta in my head".
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"I kept it together mentally, felt a bit more in control with my game too".
Four-times major champion Rory McIlroy was another to struggle, dropping two shots in his opening seven holes to drop back to three-under.
"I feel like I've been improving each day (but) I know as well as anyone that anything can happen at an Open on Sunday. But the leaderboard is packed with a lot of very, very good players". I figured I'd have to go get that number.
"I really didn't feel like I really made a bad swing until 18".
American Zach Johnson described the last four as "nasty good" on Friday while Colin Montgomerie says the finish is the "most demanding" on the Open rosta, if not anywhere. He laid up, pitched to three feet, and made a par. "Even if it's windy, as long as it's not wet, I'll try and get myself back into it".
Rose's round matched the lowest score shot in an Open Championship at Carnoustie, a traditionally hard course on Scotland's east coast.
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