Dixon, former Arsenal and England defender, will join Adrian Chiles alongside the likes of Roy Keane and Gareth Southgate.
The 48-year-old will be part of the panel for ITV's revived Tuesday night Champions League coverage from the autumn, as well as FA Cup and Europa League matches.
The respected analyst will also appear in the broadcaster's England's World Cup 2014 qualifying campaign.
Dixon confirmed his BBC departure yesterday via Twitter, saying earlier this week: "Sad to be leaving BBC. Nothing lasts forever. New challenges ahead. Loved my time there. Wonderful people."
Dixon rose to prominence when he contributed to the BBC's punditry team for the 2006 World Cup in Germany.
