The Government's Road to Zero strategy, launched last year, committed it to making all central Government cars electric by 2030, electrifying at least 25% of the fleet by 2022.
Chris Grayling has now written to colleagues across Whitehall encouraging them to play their part in transforming the overall government fleet.
Each department has received detailed guidance on how to implement their fleet's transition and is asked to publish yearly progress reports.
The Government Car Service, managed by the Department for Transport, has electrified nearly 23% of its entire fleet.
Mr Grayling said: "We want the UK to be the best place in the world to own an ultra-low emission vehicle, and as a Government we have to lead by example.
"I am pleased with the change we are making to the Government Car Service, but this now needs to be reflected in all fleets that are controlled by Government."
The Transport Secretary's move follows Prime Minister Theresa May saying there was a "moral duty" to leave the world in a better condition than "we inherited" after announcing plans for a legally binding target to end the UK's contribution to climate change by 2050.
On Wednesday, the Government was due to lay out legislation in Parliament to set a new target to cut emissions to "net zero" by the middle of the century.
The statutory instrument will amend the existing goal to cut climate pollution by 80% by 2050, which was agreed by MPs under the Climate Change Act in 2008.
"It is absolutely vital that all parts of Government play their part in delivering this ambitious target," Mr Grayling said.
Last month, the Government awarded GBP25 million to projects developing zero emission technologies for new vehicles.
Its GBP1.5 billion Road to Zero strategy aims to put the UK "at the forefront of the design and manufacturing of zero emission vehicles".
The strategy includes infrastructure support, grants for low emission vehicles and investment in research and development.
The Government has also committed to end the sale of new conventional petrol and diesel cars and vans by 2040, invest in hybrid trains, double cycling activity by 2025 and to use the GBP2.5 billion Transforming Cities Fund to improve public transport in some of England's largest cities.
The Transport Secretary has urged every Government department to support moves towards an all-electric car fleet over the next decade.