The deal marks the first time a UK broadcaster has been able to buy a collective package of UEFA Cup games, including the final.
Five will share the UEFA Cup rights with ITV and Setanta, who have also struck agreements with UEFA, European football's governing body. Five will get first pick of matches in each round.
Acting chief executive Mark White said Five owner RTL Group had put up "significant" revenue for the deal, which was a sign of Five becoming a "gold standard broadcaster".
Five is now available to at least 95% of the UK population - a benchmark needed for it to be able to bid for the right to broadcast high-profile sports events.
Under the terms of the deal with UEFA, Five will have the first pick of matches in each round and exclusive rights to the UEFA Cup Final. In total, the deal will guarantee 15 games a year from the 2009-10 season to the 2011-12 season.
For the past two years, ITV has been showing UEFA Cup matches from the quarter final onwards.