Woods is the favourite to win The Match and take home the £7m ($9m) prize fund.
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The pair are facing off in Las Vegas in a one-off match play event.
They will be making bets throughout the 18-hole round and give over proceeds to charity. Woods has donned a red t-shirt with black cardigan for The Match.
And he’s wearing his famous Nike shoes as usual.
But Woods has added an extra sparkle to his ensemble.
Tiger Woods boasts 14 major titles and seemed to reflect that in the golden Nike tick emblazoned on his shoes.
But the 42-year-old insists the gold is in fact in homage to the Las Vegas Knights ice hockey team.
“It’s a nod to not only Vegas but also the Golden Knights here,” Woods said.
“It was very appropriate to wear these here in Vegas.”
Woods and Mickelson could not be split after the first hole in Vegas.
They both holed for a Par 4 before heading to the second tee.
Discussing the match before his first shot, Mickelson said: “The tough thing when you play against Tiger, you get into his game and you watch what he does.
“In match play it’s important to know what he’s doing. For me it’s important to block that out.
“To hit shots, focus on making putts, birdies. I need to worry about executing on my end because I think why Tiger is so intimidating to so many players, and why they’ve not played their best when they’re with him is that they get caught up on watching him and what he does.
“That affects their game negatively.”