Gregan will lead a Wallabies team that contains nine rookies including props Rodney Blake, Guy Shepherdson and Benn Robinson, who have all been inducted into the national team in an attempt to regain some creditability in the front row.
Utility backs Sam Norton-Knight, Cameron Shepherd and Gene Fairbanks, loose forward Wycliff Palu, hooker Tai McIssac and scrum-half Josh Valentine also make their debut in the Wallabies team.
Valentine, the back-up scrum-half behind Sam Cordingley in the Queensland Reds, is the true bolter of the squad as he was not named in last week's 42-man train-on camp but ended up making the final 33-man line-up.
Valentine and Cordingley have both been named in the squad but will fight it out to be the bench player behind veteran scrum-half Gregan.
"There are a lot of players that are going to be exposed to this level of rugby for the first time and with a new coaching regime it sets us up for an exciting season," said Gregan.
"A lot of players in the squad had first come into the team last season and have had the benefit of another full season of Super 14, plus we have some more experienced players coming back into the squad which gives us a good balance."
Gregan's confirmation as captain under new coach John Connolly will allow him to build upon his 50 Tests as skipper and puts him in sight of the Australian record currently held by legendary lock John Eales with 55 Tests leading the line.
Brumbies skipper Stirling Mortlock and Waratahs lock Dan Vickerman have been named as the two vice-captains in the squad.
Gregan said that Australia's hectic Test match schedule will give them the perfect chance to prepare for next year's World Cup.
"We've got nine big Tests in thirteen weeks against high quality opposition in England, Ireland and three matches each against New Zealand and South Africa.
"It's a big season and that is what it's all about leading into a World Cup year," he said
Injured centre Matt Giteau was not named in the team but is expected to be rushed back into the starting line-up once he is fit to play. The champion playmaker is currently recovering from minor knee surgery.
Squad: Adam Ashley-Cooper, Al Baxter, Rodney Blake, Mark Chisholm, Sam Cordingley, Rocky Elsom, Gene Fairbanks, Scott Fava, Adam Freier, Mark Gerrard, George Gregan (capt), Daniel Heenan, Greg Holmes, Alex Kanaar, Stephen Larkham, Chris Latham, Tai McIsaac, Stirling Mortlock, Sam Norton-Knight, Wycliff Palu, Jeremy Paul, Clyde Rathbone, Benn Robinson, Mat Rogers, Nathan Sharpe, Cameron Shepherd, Guy Shepherdson, George Smith, Scott Staniforth, Lote Tuqiri, Josh Valentine, Daniel Vickerman and Phil Waugh.