The Austrian, who won the French Open in 1995, will square off against former Britain No.1 Tim Henman, 2003 Wimbledon finalist Mark Philippoussis and eight-time ATP World Tour doubles champion Colin Fleming.
Muster said: “The ATP Champions Tour gives me the opportunity to play in beautiful locations all around the world, and Gleneagles is no exception.
“I’m looking forward to playing against some top quality players, including some of the up-and-coming talent that Scotland has to offer.”
Judy Murray, mother of Scottish tennis stars Andy and Jamie, has already given her backing to the event, which will also seek to raise money for Maggie’s cancer care centres and Cancer Research UK.
The Brodies Tennis Invitational will take place on the 22nd and 23rd of June. Tickets are priced at £39.50 for adults and £20 for children.