Alistair was appointed as Chancellor of the Exchequer on 28 June 2007.

He was Secretary of State for the Department of Trade and Industry from 5 May 2006 to 28 June 2007, and Secretary of State for Transport and Secretary of State for Scotland from May 2002 to May 2006. Earlier, Alistair was Secretary of State for the Department of Work and Pensions from June 2001 to May 2002; Secretary of State for Social Security between July 1998 and June 2001, and Chief Secretary to the Treasury from May 1997 to July 1998.

Alistair was the Shadow Chief Secretary to the Treasury from July 1996 to April 1997, Opposition Spokesman on the City and Financial Services between 1992 and July 1996 and in the Opposition Home Affairs Team from 1988-92.

Alistair attended Loretto School, Musselburgh, and studied law at Aberdeen University. He worked as a solicitor in Edinburgh before being called to the Scottish Bar and admitted to the Faculty of Advocates in 1984. He has been Member of Parliament for Edinburgh Central from 1987 - 2005 and Edinburgh South West since 2005.