Scottish Government data revealed £5513 was spent on limos for the First Minister on six visits to the capital, an average of £919 per trip.
Although officials have not said what the visits concerned, some coincided with Mr Salmond's attendance at last year's Olympics and Wimbledon final.
Last month it emerged the SNP administration spends £1 million a year on the official Government Car Service, which is used ferry Scottish ministers to 10,000 engagements a year.
The amount spent on both types of ministerial limousine was more than £1.2m in 2012/13, a 12% increase on the previous year.
Mr Salmond came in for criticism in 2009 for travelling 150 yards in his chauffeur-driven car between the Scottish Parliament and Holyrood Palace to meet the Queen. The next day the Queen, then 83, made the journey on foot.
The figures revealed more than £33,000 had been spent on hotels and subsistence for the SNP leader since 2009.
A Scottish Government spokesman said it "makes appropriate arrangements for the First Minister's travel when he is undertaking official Scottish Government business in London and that has required paying either the Government Car Service or a private hire company".