The celebrity match takes place at the Beaufort Polo Club near Tetbury in Gloucestershire.
Zara said she is looking forward to the challenge.
“I’ve watched a bit of polo and played a couple of times in the past, so I know polo ponies are extremely responsive and very quick,” she said.
Joining her all-female ‘Olympic legends’ team is multi medal-winning dressage rider Laura Tomlinson, who should be able to get some tips from her professional polo playing husband, Mark.
The match will be the first for Olympic track cycling medallist now amateur jockey Victoria Pendleton, who recently tried her hand at polo alongside AP McCoy.
Heather Fell completes the line-up of Olympic legends. The modern pentathlete won a silver medal at the 2008 summer Olympics and finished that season ranked number one in the World.
She has also won multiple individual and British team medals on the European and world circuit.
“Polo is a difficult sport but great fun and I’m confident that the Olympic ladies will find our true competitive spirit and do ourselves proud,” said Zara Phillips.
AP heads the jockeys team
On the jockeys team AP McCoy is joined by John Francome, Richard Dunwoody, and Marcus Armytage, H&H’s racing columnist.
“I’ve ridden a fair few horses in my time, but I’ve only had a go at polo once and it wasn’t easy,” said AP McCoy.
Since retiring from competitive racing last year he has been playing golf so can hit a ball, but “it is a real challenge from the back of a horse”.
All the proceeds from the match and charity lunch will go to LAPResearch UK, the charity dedicated to research into diseases affecting the liver, pancreas, gallbladder and biliary tree.
The charity match is at 3pm on Sunday 19 June, the second day of the Gloucestershire Festival of Polo at the Beaufort Polo Club in Westonbirt.