Transport Scotland funding of around £1.3 million has been used by the health service to add 112 new electric cars as it bids to cut CO2 emissions.
The cars will replace the existing fossil fuelled vehicles across a number of NHS shared service functions and regions.
It will boost the number of ultra-low emission vehicles in the NHS shared service fleet by almost 80%.
Transport Secretary Michael Matheson said: "NHS Scotland is demonstrating leadership by moving at an incredible pace in taking steps to improve air quality and reduce carbon emissions through their plans to decarbonise their vehicle fleet.
"The 2019 Programme for Government outlined our commitment to phase out the need for new petrol or diesel cars in the public sector fleet by 2025 and for all other vehicles in the public sector fleet by 2030.
"This decision by the NHS directly supports that ambition and responds to the climate emergency, supporting our Climate Change Plan and our vision for Scotland's air quality to be the best in Europe - and builds on the activity already undertaken by the Scottish Ambulance Service."
Shelley MacKay, national fleet manager for NHS National Services Scotland, said: "We have worked closely with manufacturers to ensure that this new fleet of electric vehicles delivers best value for the NHS and for Scotland.
"We will continue to support the Scottish Government and work with Transport Scotland, and other partners, to achieve our shared ambition of a cleaner, greener transport future."
George Curley, director of facilities at NHS Lothian, said: "Over the coming years we plan to remove all cars and small vans that operate on petrol or diesel fuel with either electric or hybrid vehicles.
"We have a fleet of 27 electric vehicles and are gearing up to increase this to 39 by March 2020.
"A key objective for NHS Lothian is to make most of our fleet ultra-low emission vVehicles (ULEV) by 2025 and we are on course to achieve this."