The Education Minister hopes the new funding will ease the pressure on schools which, as heavy users of energy, have been hit hard by price increases by power suppliers of up to 24 per cent this year.
Schools could use the money to install solar panels and wind turbines, as well as make improvements to insulation and heating, says the Scottish Executive.
The money, which will be allocated to local authorities according to size and population, is also intended to make schools healthier places to learn.
Upgrading dining areas, payment methods for school meals, sports facilities and playgrounds will also be eligible for the cash which has been put into this year's Schools Fund, used for capital spending.
Mr Peacock said his aim was to prevent money being diverted from other resources to rocketing energy bills.
He said: "By releasing extra money, councils can make school buildings more energy efficient and our schools can concentrate their spending on books and equipment."
In Highland Council, rising energy costs have hit schools particularly badly.
Director of education Bruce Robertson wrote to headteachers at the beginning of term highlighting an increased fuel bill across his department to pound;1.5 million.
Across the council the annual energy bill rose by nearly 50 per cent from pound;3.6 million for 2004-05 to pound;6.5 million last year.
Mr Robertson said: "I see this as one of the biggest challenges currently facing us, but one where we have a huge impact to make, not just in short-term financial gain, but in the long-term educational process."
He urged schools, which along with culture and sports facilities make up 75 per cent of the council's energy cost, to look at simple ways to conserve energy.
At Nairn Academy, headteacher Jean Godden was spurred into action six months ago and since then has seen the school save a third on its bills.
She said: "When the council published the league table of energy consumption in Highland we were in the top 20."
In response the school formed an energy management group of staff and pupils.
Mrs Godden said: "The main thrust of it has been to change behaviour and learn an awareness of turning off the lights, computer monitors and closing doors. These are very simple, practical things that have made a change."
Other measures include plastic strips installed over louvred windows to save heat escaping when they are closed, and the heating system has received some extra maintenance.
Mrs Godden said: "Our janitor has been taking weekly readings of our consumption and we are saving approximately a third of our energy costs by taking these straightforward steps.
"If this is a situation we can maintain and if energy costs remain stable, we would hope that would allow the school to use the saving in other areas such as ICT."
If extra money is made available to Nairn Academy, Mrs Godden said the school would look at applying special film to higher windows in the building to save heat loss.
Another Highland school, Dingwall Primary, is to become the first school in the area to install a biomass boiler.
The existing oil-fuelled boiler will be replaced by one which will run partly on wood chips - a sustainable resource readily available in the region.
Although more expensive, the additional cost has been met with money from the council's Energy Efficiency Investment Fund plus Scottish Executive cash, and is expected to save pound;6,000 a year.