Nottinghamshire's Fiona Thornewill, 49, will join an American climber for the ascent of El Capitan mountain in Yosemite, California.
Her climbing partner American Hans Florine holds the record for the fastest ascent of the mountain.
The pair will make the climb on 8 September to raise money for the British Mountaineering Council.
Ms Thornewill set the record for the fastest ski trek to the North Pole by a woman in 2001 at 56 days and was the fastest woman to reach the South Pole solo in just under 42 days in 2004.
She was appointed an MBE in the 2006 and was given an European Women of Achievement Award in 2004.
The ascent of the steep mountain face, also called The Nose, is considered one of the most difficult rock climbs in the world as it rises almost a kilometre straight up from its base.
Ms Thornewill said she considers herself "an amateur climber" so has been training extremely hard to get ready for the attempt.
"I was looking for a physical and mental challenge since my South Pole solo - I wanted something that would really fire me up and challenge.
"I am very excited and nervous about taking it on."
If successful, she would be the oldest female ever to climb The Nose.
Mr Florine, who will be making his 100th ascent of the mountain, holds the world speed record for climbing The Nose at two hours and 23 minutes.
A record-breaking UK explorer who has already trekked to the North and South Poles is taking on a new challenge.