The money has been found from unused contingency funds for the Queensferry Crossing budget, and will mean £7m of extra investment for cycling and walking infrastructure, £2m for electric vehicle rapid chargers and £1m for up to 30 electric vehicles for car clubs.
The investments will be made over the next two years.
Transport Minister Keith Brown said: "The Scottish Government is committed to achieving the target of almost total decarbonisation of road transport by 2050.
"Cycling and walking are good not only for the individual, but they increase the safety on our roads through reduced congestion, which also helps improve our environment. This investment will help make those more attractive options.
"We do recognise that giving up the car isn't an option for everyone so we are not only investing in car clubs to help cut the number of cars on our roads, but ensuring that those cars are electric vehicles to help minimise emissions."
Mr Brown said a further £5m for the Smarter Choices Smarter Places programme, which aims to encourage sustainable travel, will be included in the draft Budget for 2015/16.
Transport Scotland plans for the investment to fund installation of up to 300 additional electric vehicle charging points, taking the total to around 1,200.