Catt has been rewarded for a magnificent season which has seen him inspire London Irish's charge into the Guinness Premiership play-offs and their European Challenge Cup final appearance.
The 34-year-old won his last international cap in the 51-15 defeat by Australia in June 2004 - Sir Clive Woodward's final match as head coach.
England will return to the Olympic Stadium with only Leicester second row Ben Kay remaining from the starting XV which overcame the Wallabies there in the 2003 World Cup final.
Sale duo Charlie Hodgson and Mark Cueto, both England regulars over the past year, have been rested while Gloucester centre Mike Tindall also misses out through fatigue.
Bath's Olly Barkley and Andy Goode of Leicester will battle it out for the number 10 jersey with Newcastle's Mathew Tait named for the first time since being dropped after winning his only cap last year.
With Leicester's Harry Ellis and Shaun Perry of Bristol unavailable to tour, Peter Richards, Nick Walshe and Scott Bemand will contest the scrum-half duties.
Richards will start as first choice for the two-Test series but Walshe has been in fine form this season, while Bemand provides back-up for Ellis at Leicester.
England's front row situation - Phil Vickery, Matt Stevens and Andrew Sheridan are all injured - has resulted in a recall for veteran Graham Rowntree.
Julian White, who featured for the British & Irish Lions in last summer's Test series against the All Blacks, is also included alongside Duncan Bell, George Chuter and Tim Payne.
Head coach Andy Robinson has named six uncapped players in an inexperienced squad - Bemand, Richards, Walshe, Alex Brown, Magnus Lund and George Chuter.
Only eight from the 22 who played against Ireland in this season's final RBS 6 Nations Championship match remain. They are Stuart Abbott, Jamie Noon, Andy Goode, Tom Voyce, Lee Mears, Julian White, Lewis Moody and Joe Worsley.
A number of big names are missing from the 30-strong touring party and Robinson confirmed he wanted to rest as many senior players as possible with the 2007 World Cup looming.
He said: "The squad for Australia is a mix of experience and youth.
"I've deliberately decided to rest some players to ensure they're in the best shape they could possibly be in ahead of the World Cup in 2007.
"I think a lot of people in the game have recognised the importance of players needing adequate rest periods once the season has finished and if necessary during the season itself.
"It's essential that the players not going on the tour have the opportunity to refresh themselves and come back to the game ready to prepare for a very challenging season for club and country.
"For those who are having operations I'd like to wish them a speedy recovery and the England medical team will be working with the club medics to ensure that they return to playing when the time is right for them.
"The tour does however give a number of players the opportunity to stake their own claims for a place in the World Cup squad and a tour to Australia will present them with one of the toughest challenges any side will face."
England squad for June's two-Test tour of Australia:
Backs: S Abbott (Wasps), I Balshaw (Gloucester), O Barkley (Bath), S Bemand (Leicester), M Catt (London Irish), A Goode (Leicester), J Noon (Newcastle), P Richards (Gloucester), J Simpson-Daniel (Gloucester), M Tait (Newcastle), M Van Gisbergen (Wasps), T Varndell (Leicester), T Voyce (Wasps), N Walshe (Bath).
Forwards: D Bell (Bath), A Brown (Gloucester), G Chuter (Leicester), L Deacon (Leicester), C Jones (Sale), B Kay (Leicester), M Lipman (Bath), M Lund (Sale), L Mears (Bath), L Moody (Leicester), T Payne (Wasps), G Rowntree (Leicester), P Sanderson (Worcester, captain), A Titterrell (Sale), J White (Leicester), J Worsley (Wasps).