The deal, negotiated by MEC, will see branding for Schwarzkopf's Live Color XXL hair-dye products appear on idents and all marketing around the Big Brother formats. The idents will be created by Signal TV.
Freederm sponsored last year's Big Brother, while Plusnet was the sponsor of Celebrity Big Brother in January.
Channel 5, Schwarzkopf and Endemol, the producer, will run a competition offering a viewer and 11 friends the chance to win "the Big Brother experience", including house voiceovers, challenges and rewards.
Ben Haxworth, the head of marketing at Schwarzkopf and Henkel, said: "The brand is all about having fun and being a bit different, so there is a great fit with Big Brother."