The First Minister revealed details of two new schemes that will help both public bodies and bus companies to increase their green vehicle fleets.
Local councils will get 4.3m to help cover the cost difference between buying normal petrol or diesel vehicles and cleaner alternatives, such as electric cars and vans.
The scheme is open to other public bodies and can be used to install battery-charging facilities for electric vehicles.
Bus companies will also get 3.4m to buy greener vehicles, such as hybrid buses that have a conventional engine and an electric motor.
The First Minister, speaking at a climate change conference in Edinburgh, said the two schemes would "significantly help public bodies and bus operators".
He went on: "The low-carbon vehicle scheme will enable local authorities and other public agencies to invest in eco-friendly vans and cars this year and help drive down air-polluting emissions.
"The green bus scheme will also provide a fresh incentive to operators to purchase eco-friendly vehicles for their fleet."
The package announced by Mr Salmond was welcomed by environmental groups such as WWF Scotland.
Dr Sam Gardner, the charity's climate change policy officer, said it was a "very welcome first step by the Scottish Government to jump-start the transformation to electric vehicles".
He said the cash would help reduce emissions, which Holyrood has agreed to slash by 42 per cent by 2020 and by 80 per cent by 2050. Dr Gardner said: "If we are to meet our challenging emission targets, the transport sector must play its full part, and that means a future where electric vehicles are the norm rather than the exception.
"The public sector has an important role to play in driving demand for electric vehicles and helping to bring them to the public's attention.
"We hope today's announcement of financial support by the Scottish Government will be backed up by committing the public sector to an entirely low-carbon vehicle fleet by 2020. This is the ambition we must see if we are to hit the targets required by the Climate Change Act."
Scotland's local government body, Cosla, also welcomed the cash boost.
Alison Hay, its regeneration and sustainable development spokeswoman, said: "The funding is very welcome and will be helpful to local authorities in establishing demonstration projects. Councils are working towards achieving a significant drop in the carbon emissions from the vans and cars we use in delivering services.
"The vehicles are currently very expensive and we need to start work on assessing the practicalities of using them.
"Our trials will help us see if the new cars and vans are cost effective and can deliver the expected savings from cheaper fuel and lower maintenance costs."
The SNP Falkirk West MSP Michael Matheson predicted the cash for bus firms would benefit Scottish manufacturers such as Alexander Dennis, which is based in his constituency.
He said: "This is good news for the workers at Alexander Dennis,
one of our leading manufacturers, specialising in the kind of new green technology needed not just in Scotland but around the world."