It capped an astonishing 12 months for the SNP leader and followed a dramatic turnaround in his political career.
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Mr Salmond was joined by Prime Minister Gordon Brown, who was named Best Scot at Westminster, as the big winners at a gala awards ceremony in Edinburgh, organised by The Herald.
Other notable winners included the billionaire philanthropist Sir Tom Hunter, who claimed the International Scot Award, and the Independent MSP Margo Macdonald, who won the Lifetime Achievement Award.
Mr Salmond, who follows his predecessors Donald Dewar and Jack McConnell in being named Scottish Politician of the Year, was awarded the title for leading his party into government for the first time in its 73-year history.
That achievement was also recognised yesterday with one of Westminster's most prestigious awards, when the Spectator named him as Parliamentarian of the Year.
In the Scottish awards, he defeated his SNP colleagues Nicola Sturgeon and John Swinney to accept the award at the prestigious Prestonfield House.
It is also a remarkable turnaround for Mr Salmond, who in 2000 received an award for Outstanding Political Achievement Award shortly after he quit the SNP leadership, when it was thought his political career was on the wane.
But after becoming SNP leader for a second time in 2004, he announced his intention to return to the Scottish Parliament, an ambition he realised on May 3 when he defeated the sitting Liberal Democrat MSP to win in Gordon.
The SNP's one seat victory over Labour saw Mr Salmond become First Minister and, in a whirlwind start to his term in office, his government has already secured the abolition of tolls on the Forth and Tay bridges, saved accident emergency departments in Ayr and Monklands and struck a deal with local authorities over a council tax freeze.
A "national conversation" on Scotland's constitutional future has also been launched, with the aim of a referendum on independence by 2010 and independence by 2017.
It is the third time that Gordon Brown has been named Best Scot at Westminster and his success comes in the year he succeeded his next door neighbour in Downing Street to become Prime Minister. He defeated Alistair Darling, his successor as Chancellor of the Exchequer, and Angus Robertson, who took over from Mr Salmond as the SNP leader in the House of Commons.
Like Mr Salmond, Mr Brown has had an eventful few months since taking over the top job in June following Tony Blair's resignation.
The terrorist attack on Glasgow Airport, which came just three days after he became PM, was an early test of his competence, as was the outbreak of foot-and-mouth disease in Suffolk.
The former chancellor's successful handling of both situations saw Labour enjoy a corresponding boost in the opinion polls, leading to fevered speculation that Mr Brown would call a General Election. But that lead over the Conservatives was whittled away after the Tories used their annual conference to unveil eye-catching policies on stamp duty and inheritance tax and the Prime Minister decided against an autumn poll.
The Editor of The Herald, Charles McGhee, said Mr Salmond's success reflected his party's incredible year.
He said: "I should like to offer my congratulations to First Minister Alex Salmond and to all our winners this evening.
"It is a reflection of how much the fortunes of the SNP have changed that three senior figures from the same party should have been short-listed for the top award, but the final decision of the judges was unanimous and the First Minister emerged as the clear winner. I would also like to thank our sponsors - Diageo, Eaga, Microsoft, Keppie Design and Ukio Bankas - for helping to make this prestigious event such a memorable highlight of the Scottish political calendar."
Meanwhile, at the Spectator political awards, the magazine's editor, Matthew d'Ancona, said Westminster's Parliamentarian of the Year award was handed to Mr Salmond in recognition of giving the Prime Minister "a kick in the teeth in his own back yard" and "a moment in history and in the annals of the Union".
Saying the SNP success "strikes at the very heart of what this country is and shall be, the judges felt it was right to salute the man whose brilliant tactics in the Scottish Parliament laid the foundations for an extraordinary victory".
Michael Connarty, Labour MP in Linlithgow and East Falkirk, was named Inquisitor of the Year at Westminster and Politician of the Year was George Osborne, the Shadow Chancellor.
Lifetime Achievement Award WINNER: Margo Macdonald. Scottish Politician of the Year WINNER: Alex Salmond (SNP), For a historic breakthrough election victory in May. Runners-up: Nicola Sturgeon (SNP) and John Swinney (SNP). Best Scot at Westminster WINNER: Gordon Brown (Lab), for his unchallenged rise to become Prime Minister. Runners-up: Alistair Darling (Lab) and Angus Robertson (SNP) Donald Dewar Debater of the Year WINNER: John Swinney (SNP), Robust in opposition and better still in government. Runners-up: Tavish Scott (Lib Dem) and Nicola Sturgeon (SNP). (Award sponsored by eaga). One to watch WINNER: Derek Brownlee (Con), a recent arrival at Holyrood, already in a key Tory role. Runners-up: Jackie Baillie (Lab) and Elizabeth Smith (Con). (Award sponsored by Microsoft). International Scot Award WINNER: Sir Tom Hunter, retail tycoon turned big league philanthropist. Runners up: Black Watch, National Theatre of Scotland and the Tartan Army. (Award sponsored by Keppie Design). Free Spirit of the Year WINNER: Christine Grahame (SNP), never one to be told what to think or say by the SNP whips. Runners-up George Foulkes (Lab) and Margo MacDonald (Ind). Public Campaign of the Year WINNER: Farepak savers' campaign, for reclaiming Christmas for thousands of let-down savers. Runners-up: Haemophilia Forum and ICL Plastics/Stockline Family Support Group. (Award sponsored by Uko Bankas). THE JUDGES Charles McGhee, editor of The Herald; Douglas Fraser, The Herald; Iain Macwhirter, The Herald; Paul Hutcheon, Sunday Herald; Colin Mackay, Emap Radio; Joe Quinn, Press Association; Brian Taylor, BBC Scotland. Online Coverage