Woods and Justin Thomas will face the International Team's Marc Leishmann and Joaquin Niemann as Australia's Royal Melbourne course prepares to take centre stage.
"It was important for me to get out there as a player, but also as a captain, I want to obviously see my guys play," Woods told www.pgatour.com.
"This is my first time as a captain. I want to be able to enjoy that part of it as well."
Thomas will be Woods' 11th different Presidents Cup partner, while Leishmann is among three Australians in Ernie Els' International select.
Match two sees Patrick Cantalay and Xander Schauffele face Adam Hadwin and Sungjae Im, before America's challenge is continued by Bryson Dechambeau and Tony Finau taking on Adam Scott and An Byeong-hun.
The fourballs continue with Webb Simpson and Patrick Reed meeting Hideki Matsuyama and C.T Pan, then Dustin Johnson and Gary Woodland take on Abraham Ancer and Louis Oosthuizen.
Rickie Fowler and Matt Kuchar sit out the American team's initial fourballs action, with Els not using Cameron Smith and Haotong Li.
Els, meanwhile, paid tribute to Woods as the pair prepare to lock horns in a captaincy capacity.
"He's one of the best, the best of my generation," Els told www.presidentscup.com.
"It was a privilege to compete against him.
"I know I would have had a couple more events under my belt, but still very proud to have played with and against Tiger. To be friends with him is another privilege.
"Where the game of golf has gone in the last 25 years is just remarkable, and it could not be where it is today if it wasn't for Tiger Woods."
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