The team will be responsible for growing revenue from sponsorship, interactive, joint ventures, telephony, licensing and merchandising.
Jon Lewis, five's former head of sponsorship, takes the new role of head of commercial development and will report to five's executive director of sales, Mark White, and its sales director, Kelly Williams.
Five has also appointed Emma Derrick, the former head of commercial development, to be the commercial development controller.
The broadcaster is creating the team because it will find it increasingly difficult to grow its share of TV ad revenue, which stood at 8.1 per cent in 2003, with growing competition from multichannel.
Other members of the team include Adam Strange, the commercial revenue manager; Damon Letzer, who heads interactive advertising, and the sponsorship manager Rachael Wheeler.
Lewis said: "With five now very much part of the television mainstream and broadcast technology developing so quickly, opportunities to utilise our brand strength have become increasingly prevalent."