The move has been described as a "historic moment" in the UK's transition away from fossil fuels and towards achieving net-zero climate goals.
Longannet in Fife, which closed in 2016, was the largest power station of its kind in Europe, according to ScottishPower. The first minister hit the button to ignite 700kg of explosives to blow up its chimney, bringing down the curtain on the site more than 50 years after it was first opened.
Scotland has been coal-free since ScottishPower closed and the energy company now generates 100 per cent green electricity through its wind and solar farms.
Ms Sturgeon said the event was a "symbolic reminder" that Scotland had ended coal-fired power. "Our goal is to generate 50 per cent of overall energy consumption from renewable sources by 2030, and Scotland's energy sector is well placed to deliver on the key investments in renewables, hydrogen and energy storage required to achieve this," she said.
"Growth in these sectors over the next decade will be transformative for Scotland, delivering further good, green jobs, strengthened energy security, and benefits for local communities as we decarbonise industry and society to mitigate the worst effects of climate change, in a way that leaves no-one behind," the first minister added.
Lang Banks, director of the World Wife Fund for Nature Scotland branch, said: "It's a historic moment to see the chimney of Scotland's last coal-fired power station come down. "We have successfully made coal power history in Scotland and rapid progress is now being made globally towards cleaner, renewable energy."
Longannet began generation in 1970. At the height of operations, it burned coal from around the world including from as far away as Russia and Colombia, as well as from Scottish open-cast mines.
Typically, it consumed four million tonnes of coal per year and at full production could make enough electricity to power two million homes.
Keith Anderson, chief executive of ScottishPower, said: "At Cop26 in Glasgow, we were proud to show the world that Scotland has already made coal history.
"As a 100 per cent energy company, we are committed to helping the UK end its reliance on fossil fuels. For half a century, Longannet's chimney has dominated the Firth of Forth skyline. We bade farewell to that landmark today - however this is a landmark day for Scotland too."
He added: "Watching the chimney of Scotland's last coal-fired station fall today represents a real milestone, as the UK moves away from the large polluting power stations of the past and accelerates down the road to net-zero emissions.
"We already know the transition from fossil fuels to renewable energy is essential to minimise the worst impacts of global warming and address the climate emergency."
The demolition of Longannet is being carried out by ScottishPower contractor Brown and Mason and work to remove materials at the site will continue into 2022.
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