Graeme Cadger, chairman of Murray's testimonial committee, confirmed that former France World Cup-winner Pires would be among the players taking part.
"We are delighted Robert has accepted our invitation and we look forward to welcoming him to Easter Road," he said.
All sponsorship and hospitality packages for Sunday are sold out. However a limited number of VIP Tickets are available for the Edinburgh Suite.
A free prize draw for all VIP ticket holders will be made on the day with the winner receiving a Hibs strip signed by Vieira, Pires and Murray.