Legends of the game will be present at the tournament next month.
Tom Watson and Ian Poulter will both take part in the Berenberg Gary Player Invitiational next month.
Watson, an eight-time major winner, and Poulter are among those to complete the line-up at the event at Wentworth.
The tournament, which takes place on July 20th, have also confirmed the presence of Louis Oosthuizen, after his runner-up finish at the US Open.
Padraig Harrington, Branden Grace, Ian Woosnam and Hunter Mahan will also be amongst those teeing it up next month.
This year commemorates the 50th anniversary of Player's completion of his Grand Slam, which he sealed by winning the US Open in 1965.
Player said: "I'm overjoyed that so many stars are joining us in the Union of Golf and Giving at this historic time."
Money raised from the event will be given to Depaul UK, a charity that helps young homeless people.
Player added: "We have already raised more than $60million for charities worldwide and look forward to adding to that on July 20th at the historic Wentworth Club in London."
Earlier this month, Fred Couples and Mark O'Meara were confirmed to be in the field, alongside current Tour players Zach Johnson, Jason Dufner and Charl Schwartzel.
Players from the women's tour will be in attendance, including Britain's Charley Hull, Melissa Reid and Amy Boulden.
Russia's first Ladies European Tour member Maria Balikoeva and Manulife LPGA Classic winner Suzann Pettersen will also take part.
As well as professional golfers, there will be celebrity guests too, including DJ Jonathan Joseph and songwriter Brian McFadden.
Sponsor Berenberg will be celebrating their 425th anniversary during the event.
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