The veteran London Irish centre, who was voted Guinness Premiership player of the season on Wednesday night, last started an England home game against South Africa in November of 2001.
Catt is paired in the centres with Newcastle's Mathew Tait for Sunday's non-cap game, while Mark Van Gisbergen is awarded his first start in an England jersey at full-back.
The side is captained by Worcester's Pat Sanderson who starts at number eight - an indication of how head coach Andy Robinson plans to utilise his skipper on next month's Test tour of Australia when he will be without both Lawrence Dallaglio and Martin Corry.
Robinson is without his Leicester and Sale contingent as they prepare for Saturday's Guinness Premiership Grand Final.
He has supplemented the squad for Sunday's game with players from the England Saxons' Barclays Churchill Cup party - Gloucester's James Forrester starts on the blind-side flank and James Hudson comes into the second row.
Iain Balshaw and James Simpson-Daniel start on the wings with Olly Barkley, who missed the RBS 6 Nations Championship through injury, the starting fly-half alongside scrum-half Peter Richards.
"I am excited about the side we have selected," said Robinson.
"There is a good blend of experienced internationals such as Iain Balshaw and Mike Catt, as well as guys we are looking to develop through the Churchill Cup like James Hudson and James Forrester.
"Playing a strong Barbarians side will be an ideal test before we go to Australia and the Saxons to Canada and I am confident that, ably led by Pat Sanderson, they can win on Sunday."
Catt last pulled on an England shirt in the 51-15 Test defeat to Australia in 2004 but has been instrumental in London Irish's successful season.
Robinson recalled Catt after two years in the international wilderness because he believes the 34-year-old can play a mentoring role to the youngsters in England's touring squad.
When announcing his tour squad 10 days ago, Robinson said: "By bringing the new players in we have, it was important to have a player in that could work with them.
"The key for me is that Mike Catt can translate to the younger players the type of game we are looking to play over there.
"The players can bounce ideas off him and chat to him. As he has shown with London Irish this year. The players can play around him and have that confidence to play with him."
Teams for Gartmore Challenge match between an England XV and the Barbarians, Twickenham, Sunday, 3pm.
England XV: M Van Gisbergen (Wasps); J Simpson-Daniel (Gloucester), M Tait (Newcastle), M Catt (London Irish), I Balshaw (Leeds); O Barkley (Bath), P Richards (Gloucester); T Payne (Wasps), L Mears (Bath), D Bell (Bath), J Hudson (Bath), A Brown (Gloucester), J Forrester (Gloucester), M Lipman (Bath), P Sanderson (Worcester, capt).
Replacements: D Paice (London Irish), D Barnes (Bath), K Roche (London Irish), J Haskell (Wasps), S Bemand (Leicester), S Abbott (Wasps), D Armitage (London Irish).
Barbarians: M Burke (Newcastle); B Reihana (Northampton), T Castaignede (Saracens), D Feau'nati (London Irish), J Roff (Kubota); C Spencer (Northampton), M Robinson (Northampton); A Lo Cicero (L'Aquila), R Ibanez (Wasps, capt), C Visagie (Saracens), B Casey (London Irish), T Palmer (Leeds), X Rush (Cardiff Blues), O Magne (London Irish), T Kefu (Kubota).
Replacements: (from) M Regan (Bristol), P Bracken (Wasps), D Leo (Wasps), S Harding (Northampton), J Marshall (Ospreys), D Humphreys (Ulster), I Nacewa (Auckland), F Waters (Wasps), D Hewett (Edinburgh), O Finegan (Newcastle).
Referee: Donal Courtney (Ireland).