Peter Collins, a one-time senior member of the NSW Liberal Party, will become chairman of lobby group Industry Super Network.
Mr Collins will next week replace former Labor premier of Victoria Steve Bracks, who has been appointed Australian consul-general in New York.
Mr Collins is deputy chairman of ISN, which represents the non-profit superannuation sector and its estimated 5 million members. According to the latest figures, industry funds account for 20 per cent of Australia's $1.62 trillion retirement savings pool.
In his political life, Mr Collins served as minister for health, attorney-general and treasurer in the NSW Greiner/Fahey government, and as deputy leader and leader of the opposition before leaving Parliament in 2003. He is now a director of the industry super fund Hostplus.
The deputy chairman of the ISN will be John Brumby, Mr Bracks' successor as premier. Mr Brumby now serves on the Australian board of Chinese telco Huawei and as chairman of industry super fund MTAA Super.
ISN chief executive David Whiteley said Mr Collins and Mr Brumby had "held highly esteemed positions in public office and have a demonstrated commitment to our guiding principle of putting the interests of members first".
Mr Collins said Australia's super system was "the envy of the world, and should remain so. ISN will continue to provide much-needed leadership by standing up for our super system and safeguarding Australia's retirement savings."
ISN and retail lobby group the Financial Services Council, representing big banks and fund managers such as AMP, recently said they would put aside their differences and work to influence government policy on superannuation. The council is led by former Liberal politician John Brogden.
Retail, or "for-profit", funds have traditionally criticised the appointment of union representatives to industry funds. In turn, industry funds have pointed to their outperformance of retail funds over the long term and their lower fees.
The super industry has had some big wins in the past few years, including raising of the compulsory super guarantee to 12 per cent, self-managed super funds being able to borrow to buy property and pledges from Labor and the Coalition not to introduce changes to the taxation of super in the next term.