The nine-month partnership will promote a variety of Sky channels and programmes during the Real Radio breakfast shows between 6am and 9am, through a mix of 60-second on-air features and sponsorship credits.
In addition to the sponsorship of breakfast programming, Real Radio stations will air 60-second features during drivetime shows, as well as three on-air promotions and branding on station websites.
In November, the activity, which was planned and bought by MediaCom, will promote programmes from the Sky 1, Living, Sky Arts, Sky Atlantic, FX, History, Discovery and Eden pay-TV channels.
All creative will be produced by Real Radio's in-house teams.
The sponsorship will complement the deal Sky kicked off with Magic 105.4 yesterday (30 October). The Magic activity includes sponsorship of Magic's drivetime show and sponsored features at breakfast.
Bob Suppiah, director of promotions and partnership marketing for BSkyB, said it would use the sponsorship to "showcase the breadth of quality entertainment on Sky".
The Real Radio network includes stations in Scotland, the North East, the North West, Wales and Yorkshire.
John Walker, sponsorship and promotions director at Real Radio's parent group Real and Smooth Ltd, said: "This is the first time we have created a network breakfast sponsorship for Real Radio and we are delighted to welcome one of Britain's strongest entertainment companies onto our stations as a sponsor.
"Real has an extremely powerful presence in the lives of families in large regions of the country, as well as Wales and Scotland, so we look forward to working with Sky to promote its programmes and channels in the coming months."
Earlier this month, Real and Smooth Ltd announced plans to introduce networked shows on the Real Radio stations in between breakfast and drivetime, as part of a wider restructure of the group.
Walker said that in future, the networked daytime shows will allow brands to "not only reach much of 'middle England', but 'Middle Britain' on one network of radio stations".
Real and Smooth Ltd, formerly known as GMG Radio, was bought by Global Radio in June and the Competition Commission launched an investigation into the merger earlier this month.