The firm was in the frame to become the sponsor of the programme, replacing Carphone Warehouse, which ditched its £3m sponsorship package earlier this month.
The Carphone Warehouse severed its ties with the show in the wake of the racism row cantering around the treatment of Bollywood star Shilpa Shetty by fellow housemates Jade Goody, Danielle Lloyd and Jo O'Meara
The mobile phone retailer dumped its interests in the main strand of the reality show and its celebrity spin off. However, it has said it will still run spot advertising when the show airs.
Orange had been linked with the sponsorship along with a series of other high-profile brands, including Toyota, Unilever's Lynx brand and mobile phone retailer Phones4U.
A spokesman for Orange said: "We asked our staff what they thought about sponsoring 'Big Brother' as we like to get them involved in the decisions their companies makes. In this case, the majority of our staff felt that we should not sponsor Big Brother.
"Having taken this into consideration, and having evaluated it further with our sponsorship team, we have declined the opportunity."
The programme is to return with its eighth series this summer, with a permanent sponsor still to be found.
The activity includes branding and advertising opportunities across TV, video-on-demand, online, radio and mobile.
Channel 4 said that it hoped to announce new sponsor within the next two months.
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