The broadcaster will be airing the first episode of the hit 1960s ad agency drama since 2010 and its first since picking up the rights for the critically-acclaimed drama from AMC.
As part of the premiere launch, Sky Atlantic will treat fans to special advertisements, which will move through time during the breaks.
Adverts confirmed to air during the broadcast include the original Flake girl commercial, Prunella Scales's Tetley Tea promo, a Milk Tray man advert, Tony Hancock's 'Go To Work with an Egg' spot, Citroen, Birdseye and Fairy Liquid promos.
Sky Media's managing director Nick Milligan said: "Taking our inspiration from the series, we wanted to give our viewers the opportunity to enjoy adverts from the era of Mad Men and to create real event programming. I'm delighted with the response we've had from the industry."
Mad Men season five launches tonight at 9pm on Sky Atlantic.
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Watch the classic Fairy Liquid advert that will air during tonight's Mad Men below: