Alston was educated at Xavier College (Kew), the University of Melbourne and Monash University, graduating with bachelor"s degrees in law, arts and commerce from Melbourne University and master"s degrees in Law and Business Administration from Monash University.
He is currently the Federal President of the Liberal Party of Australia. He was a barrister before entering politics. On 7 May 1986 Alston was appointed by the Parliament of Victoria under section 15 of the Australian Constitution to fill the vacancy in the Australian Senate caused by the death of Senator Alan Missen.
He was re-elected in 1987, 1990, 1996 and 2001.
Shadow Minister for Social Security, Child Care and Superannuation,as well as Communications and the Arts, were among the positions he held in the shadow ministry. He was Minister for Communications and the Arts 1996-1997, Minister for Communications, the Information Economy and the Arts 1997-1998 and Minister for Communications, Information Technology and the Arts 1998–2003.
He was also Deputy Leader of the Government in the Senate 1996–2003. Alston resigned from the Senate on 10 February 2004, and he was replaced by Mitch Fifield.
From February 2005 to February 2008, Alston served as Australian High Commissioner to the United Kingdom.
Since 2004 he has been an Adjunct Professor of Information Technology at Bond University. Since leaving Parliament, Alston has served as a non executive director of Australian public listed companies.
Alston was a member of the Opposition Shadow Ministry from 1989 to 1996, and was Deputy Leader of the Opposition in the Senate 1993-1996. He is currently Chairman of American Experience Limited, a listed Australian resources company, a member of the global advisory board of London-based hedge fund CQS Limited Liability Partnership, Chairman of the China-based Waratah Group, a director of CQS Investment Management (Australia) Pty Limited, Nanuk Asset Management Pty Limited, and Balmoral Gardens Pty Limited, as well as a member of the national Board of Certified Public Accountants Australia.
Married; 2 children.