NSW Premier Barry O'Farrell, NSW Tourism Minister George Souris, Football Federation Australia CEO David Gallop and ex-Manchester United and Sydney FC star Dwight Yorke were on hand to make the significant announcement.
The world's richest and most famous football club had been in talks with FFA for months with a deal believed to be worth $3 million sealed for Sir Alex Ferguson's men to head Down Under as part of their 2013 pre-season tour.
The match will be played at ANZ Stadium - formerly Stadium Australia - where the Red Devils last played in Australia in 1999.
Organisers said Manchester United would bring its full squad for the match with Wayne Rooney, Robin Van Persie, Rio Ferdinand and Nani set to play in front of an expected sell-out crowd.
"I'm delighted that the NSW Government's agency, Destination NSW, in partnership with ANZ Stadium, has won an Australian and New Zealand exclusive to host Manchester United in NSW, the home of world class sport," NSW Premier O'Farrell said.
"Manchester United is the most successful English football club in history, having won 19 Premier League titles, 11 FA Cups and three European Cups, and the match against our A-League team promises to be an exhilarating contest.
"I invite Manchester United fans and football fans across the world to come to Sydney to enjoy the best in world football, in Australia's premier sports and major events city."
The club last played in Australia against the Socceroos in both Sydney and Melbourne, but big names including the likes of David Beckham, Paul Scholes, Gary Neville and manager Sir Alex Ferguson were left at home.
However, veteran Ryan Giggs could make a return visit after being part of United's touring party more than 13 years ago along with Mark Bosnich and Yorke.
The A-League team will be selected by fans and could feature the likes of Sydney FC marquee man Alessandro Del Piero, Brisbane's Thomas Broich and Besart Berisha, Perth's Shane Smeltz and Melbourne Victory's Marcos Flores.
But local players with Socceroos commitments, including Brett Emerton and Archie Thompson, would be unlikely to feature with the match clashing with the East Asian Cup, which Australia qualified for on Sunday.
The match is expected to generate an even greater level of hype than the 2007 visit of Beckham's Los Angeles Galaxy - with Premier O'Farrell predicting a $16 million boost to the NSW economy during United's five-day visit.
That Galaxy match, played in front of more than 80,000 fans, gave the local game a huge boost and officials are hoping next year's fixture will build further on the hype generated by marquee stars Del Piero and Newcastle's Emile Heskey this season.
United, which has won a record 19 league titles, sits top of this year's Premier League by six points after a 3-2 win over city rival Manchester City.
Ferguson's side will play only the one match in Australia as part of its build-up to the 2013-2014 EPL season.
"Having Manchester United as the opponent for our first ever A-League All Star game will put the A-League on the world stage," FFA chief executive David Gallop said.
"I'm absolutely delighted Australian fans will get to see the Red Devils in action against the best A-League players.
"It's a massive opportunity for our players and one the fans won't want to miss."
Tickets for the match are on sale to Football Family members on Tuesday and the general public on Wednesday.
Let us know who you would select in your A-League XI in the comments below.