The royal is taking part in a 335-kilometre (210-mile) race between three teams of four wounded military personnel, representing Britain, the United States and the Commonwealth (drawn from Australia and Canada).
The 29-year-old army attack helicopter pilot will trek alongside the British team in the charity race to the planet's southernmost point, which is expected to take 16 days.
After arriving in Cape Town on a flight from London, the teams were to fly on Tuesday to the air base by Russia's Novolazarevskaya Station, at the edge of the Antarctic continent.
Once acclimatized to the altitude and freezing temperatures, the teams hope to begin the race on November 29. They aim to reach the South Pole around December 17.
Each team has a mentor and a polar guide. Harry is patron of organizers Walking With The Wounded, which raises funds to retrain injured troops and help them find new careers outside the military.
He launched the charity's South Pole Allied Challenge in London's Trafalgar Square on Thursday.
"All the men and women behind me have achieved so much just to get here, let alone actually walk to the South Pole," he said, flanked by the competitors.
He added, "This trip is another way of reminding everybody that as Afghanistan draws down and these guys aren't in the news any more the support must continue."
Trekking around 20 kilometers per day, the teams will be pulling 70-kilogramme (155-pound) sleds.
They will likely endure temperatures as low as minus 35 degrees Celsius (minus 31 degrees Fahrenheit) and wind speeds of around 50 miles (80 kilometers) per hour.
Speaking at London Heathrow Airport yesterday before departing, British army veteran Ibrar Ali, whose right arm was amputated after a roadside bombing in Afghanistan in 2007, felt both nervous and excited about the challenge ahead.
"A bit like pre-tour when you're just about sat at Brize Norton (airbase) when you're just about to go out to Iraq or Afghanistan," he said.
Speaking of Harry's involvement, he added: "He's a great team member and just fits in really well so no different to anyone else." 


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