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The third-in-line to the throne, who is 28, will set off in November for the 335km charity race against injured troops from the United States, Canada and Australia.
The prince, an Apache helicopter pilot who has served in Afghanistan, said the veterans aim to "meet a challenge head-on and overcome it - and inspire others to do the same".
"These men and women have given their all in the cause of freedom," he told a press conference in London on Friday.
"That they should once again step into the breach - this time facing down the extreme physical and mental challenges of trekking to the South Pole - just underlines their remarkable qualities."
Showing his competitive streak, he warned the other teams with characteristic humour: "As a member of the British team, I will have a brew (a cup of tea) ready for you when you join us at the Pole."
Harry is patron of the South Pole Allied Challenge race, and of the charity Walking With The Wounded which is sending the British team to Antarctica.
He trekked part of the way to the North Pole with the charity in 2011 but came home early to attend the wedding of his brother Prince William and Kate Middleton.
He also missed out on a bid to conquer Mount Everest last year because of military commitments ahead of his second tour in Afghanistan.
The prince returned to Britain from the four-month tour in January. He stirred controversy by saying he had killed Taliban fighters in Afghanistan's restive southern Helmand province, where he flew scores of missions as a helicopter gunner.
