Finance Secretary John Swinney said the money is being made available by extending the Non-Profit Distributing (NPD) method of funding.
He also revealed an additional £31.2 million will be invested over the next two years to help provide the infrastructure needed for an expansion of childcare.
This cash will go to local councils, along with an extra £12 million towards the provision of free school meals for pupils in primaries one to three.
A further £10.3 million is going to the Scottish Government's Help to Buy (Scotland) scheme - which assists those buying a new build home - in 2014-15, while another £12 million is to be invested in measures aimed at helping young people into work, such as the modern apprenticeship scheme.
In addition, £1 million will be spent both this financial year and next financial year to help mitigate the impact of UK Government welfare reforms, Mr Swinney told MSPs.
"We cannot undo all of the damage of welfare reform, the austerity agenda or the consequences of Westminster's economic mismanagement," he said.
"The actions of this Government demonstrate however our determination to take the initiative where we can."
But the announcement of additional cash for childcare and free school meals sparked claims from the opposition that the Scottish Government had failed to fully fund these.
Mr Swinney's budget for 2014-15 included funding to provide more free childcare places, along with money for free school meals.
Labour finance spokesman Iain Gray said at the time the Finance Secretary had been "adamant then that he had fully funded those commitments".
But he said the allocation of additional money was "a straightforward admission that the commitments made in January were never fully funded".
Tories and Liberal Democrats also pressed Mr Swinney on the cash for childcare.
Conservative finance spokesman Gavin Brown said the Finance Secretary had "stated that we still don't understand the capital cost implications of childcare expansion".
Mr Brown hit out: "This was a policy announced months ago, if they don't understand the cost implications when does he envisage they will understand the capital implications of that policy?"
Liberal Democrat leader Willie Rennie said: "I want to bring childcare provision in line with that of England's where 40% of two-year-olds, beginning with those from poorer backgrounds, benefit from free childcare.
"Two-year-olds cannot wait forever. John Swinney must tell parents when he will listen to my calls to build a fairer society and expand free childcare so that more children are given the best start in life."