The intrepid stars started their ascent of Africa's tallest mountain at 0600 local time (0300 GMT), a spokeswoman for the expedition said.
The nine-strong group, including Girls Aloud's Cheryl Cole and Radio 1 DJ Chris Moyles, are raising cash for this year's Red Nose Day Campaign.
It will take them eight days to reach the summit of the 19,340ft mountain.
Speaking before they set off, spokeswoman Kristina Kyriacou said: "They've had a briefing from Jeremy Gane, a tour operator who is leading the climb - it will be the 21st time he has climbed the mountain.
"They've also had briefings from two doctors who will go with them.
"They will trek through the rainforest, where it will be very hot and humid - they won't go any faster than the slowest person. It should take three days to get to base camp."
The celebrity BT Red Nose Climb team boarded a Kenya Airways flight on Friday evening for their 10-day expedition.
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