The betting exchange will be the Official Betting Partner of the Catalan club and will generate sports betting content through its official website.
Betfair branding will also be visible on perimeter boards at the club’s Camp Nou stadium.
The agreement follows the three-year deal the betting firm signed with English Premier League champions Manchester United in August.
The partnership was the first Betfair had agreed with a football club since its one-year shirt deal with Fulham in 2003.
It has previously concentrated its efforts on cricket and horse racing.
To support the football partnerships, Betfair has created a dedicated football website, www.betfairfootball.com.
Rival 188BET has also been stepping up its football sponsorship activity, recently signing two official partnership agreements with Aston Villa and Chelsea and two shirt sponsorship deals with Bolton Wanderers and Wigan Athletic.