The opening double bill of the new 12-part limited series will be shown at 1am on Sky1 in the early hours of Tuesday, May 6 - the same time that it airs in the US (Monday, May 5 on Fox).
The drama will subsequently air in a regular Wednesday night slot at 9pm from May 7 onwards, at which point the episodes will be available to catch up On Demand.
Jack Bauer's latest adventure, set and shot in London, sees Kiefer Sutherland's fugitive working to thwart a drone attack on the visiting president of the United States.
Sutherland will be joined by fellow 24 veterans Mary Lynn Rajskub, Kim Raver and William Devane. New cast additions include Tamer Hassan, Stephen Fry, Yvonne Strahovski and Colin Salmon.
Sky1 boss Adam MacDonald said: "I'm delighted that Jack and the team at 24 are returning exclusively to Sky1 HD.
"The scale, ambition and fast-paced energy of the series epitomise everything we look for in a drama for the channel. I can't wait to bring it back to our customers."
It follows Sky's simulcast of the opening episode of Game of Thrones' fourth season this weekend.
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Watch a promo for 24: Live Another Day below: