Woods, who last slipped on the Green Jacket in 2005, will start Sunday’s final round with Molinari and Tony Finau after tee-times were moved forwards due to the threat of thunderstorms.
Italian Molinari, who leads the way on 13-under 203, is unlikely to be intimidated by Woods, after staring down and overtaking the American en route to winning last year’s British Open at Carnoustie, where they were paired in the final round.
A victory on Sunday would be Woods’ fifth at Augusta National, leaving him second behind six-times champion Jack Nicklaus, but to do so he will have to pull off something he has never done before - come from behind in the final round to win a major.
All 14 of his major wins have come after Woods held the 54-hole lead.
Masters Tee Times: Sunday’s Final Round (BST)
Tee No. 1
12:30 – Aaron Wise, Marc Leishman, Si Woo Kim
12:41 – Matthew Fitzpatrick, Kevin Tway, Patton Kizzire
12:52 – Henrik Stenson, Hideki Matsuyama, Cameron Smith
13:03 – Jordan Spieth, Tommy Fleetwood, Corey Conners
13:14 – Jason Day, Bubba Watson, Lucas Bjerregaard
13:25 – Justin Thomas, Phil Mickelson, Jon Rahm
13:36 – Adam Scott, Patrick Cantlay, Thorbjorn Olesen
13:47 – Louis Oosthuizen, Dustin Johnson, Rickie Fowler
13:58 – Matt Kuchar, Justin Harding, Xander Schauffele
14:09 – Brooks Koepka, Webb Simpson, Ian Poulter
14:20 – Francesco Molinari, Tony Finau, Tiger Woods
Tee No. 10
12:30 – Kyle Stanley, Viktor Hovland (A), Charley Hoffman
12:41 – Kevin Kisner, Bryson DeChambeau, Takumi Kanaya (A)
12:52 – Rory McIlroy, Keegan Bradley, Gary Woodland
13:03 – Jimmy Walker, J. B. Holmes, Charles Howell III
13:14 – Kiradech Aphibarnrat, Kevin Na, Alvaro Ortiz (A)
13:25 – Patrick Reed, Devon Bling (A), Keith Mitchell
13:36 – Tyrrell Hatton, Satoshi Kodaira, Andrew Landry
13:47 – Bernhard Langer, Rafael Cabrera Bello, Eddie Pepperell
13:58 – Branden Grace, Martin Kaymer, Haotong Li
14:09 – Emiliano Grillo, Zach Johnson, Billy Horschel
14:20 – Trevor Immelman, Alex Noren