At a press launch yesterday, ITV confirmed that Adrian Chiles would lead the team in Poland and Ukraine as presenter, aided by long-time pundit Gareth Southgate.
They will be joined by Vieira and Keane, who often clashed during their Premier League playing careers at Arsenal and Manchester United respectively.
Jamie Carragher, the Liverpool defender, completes the ITV Sport team for the tournament, which gets under way next month.
ITV will share the UK coverage rights to Euro 2012 with the BBC, as both broadcasters have committed to running live coverage of all 31 games from the tournament on TV, online and on mobile.
ITV will kick off England's campaign with the group stage clash against France on June 11. The BBC will show the middle group game against Sweden on June 15, and ITV will close the pool stage campaign with the match against the Ukraine on June 19.
Should England make it out of the group, the BBC will broadcast the team's first knockout match. The final, on July 1, will be shown simultaneously on BBC One and ITV1.
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ITV has also launched a new advertising campaign for the coverage, which rewrites the key moments of agonising failure for England at previous Euro tournaments.
The clips include Southgate actually scoring his penalty at Euro 96, and former England manager Steve McLaren watching as his team secures the point they needed to reach Euro 2008.
Another clip imagines Tomas Brolin failing to score against England in 1992, although ITV was not quite able to edit out Martin Dahlin celebrating the 'miss' in the foreground.
Watch the clips below: