The five year deal, thought to be worth about £3m a year, will see BSkyB become a "founding partner" of the O2 alongside brands including Adidas, BMW and Coca Cola.
Sky has signed the deal with AEG Europe, which took over the former Millennium Dome in 2005 and rebranded and relaunched the venue as the O2, as the exclusive partner for TV, home broadband and telephony.
The deal gives Sky first refusal on TV and online broadcast rights for most music gigs and other adventure at the location.
Sky will also have access to media and advertising space across the Greenwich venue, including at the 3D cinema. All screens at the O2 will be converted to high definition and used to demonstrate the company's Sky+ HD product.
The broadcaster will launch a reward programme to give Sky customers VIP access to adventures and screenings at the O2.
"Thanks to the venue's scale of reach, we are working with AEG to create a number of branding, exhibition and customer engagement opportunities that no other single entertainment location can offer," said the managing director of Sky's customer group, Brian Sullivan. "We will use this relationship to both absorb new conference and reward our valued customers."