Around £1.2 million was spent in 2012-13, compared with almost £1.1 million the previous year.
Private hire vehicles accounted for £159,612, up from £99,584 in 2011-12 and £46,081 in 2010-11.
The Government Car Service (GCS) is said to have cost £1,045,252 last year, up from £975,130 in 2011-12.
GCS and private hire cars were used to make 10,389 journeys last year, up from 9,201 the previous year.
GCS provides transport for Scottish ministers and ministers of other UK administrations when they are in Scotland. It can also be used by the lord advocate and solicitor general, the Permanent Secretary of the civil service, dignitaries and advisers with the approval of ministers and, where necessary, for transporting official documents.
Private car hire companies are used when GCS cars and drivers are not available.
Commenting on the increase in spending, Conservative deputy leader Jackson Carlaw MSP said the use of the car service and private vehicles is at odds with the Government's push for sustainable transport.
"On the one hand you have ministers telling people to hop onto their bikes and leave the car at home. On the other their spending on being ferried around in plush vehicles has soared," he said.
"It's more evidence of a grey-haired, male-dominated frontbench, so fatigued by the challenges of government they can't even face travelling in any other fashion except the extortionate. This is a drain on taxpayers, many of whom are being made to feel ashamed by the SNP for simply driving to the supermarket."
A Scottish Government spokesman said: "We continually looks for ways to minimise the use of cars for official journeys and ensure that the Government Car Service is delivered in the most cost-effective manner. However, GCS costs have been impacted by increasing fuel costs which have doubled since 2006-07. Ministers car-share whenever practicable.
"Use of private car hire is avoided where possible. The increase in these costs has primarily been because of a lack of driver availability due to long-term staff sickness."