Nicola Sturgeon's ministers have said no more of their money should be given to the Ukraine for weapons after being pressured by the Treasury to hand over £65 million.
Kate Forbes, the Scottish Finance Secretary, said she had agreed to provide the money "on this occasion" but lashed out at the Treasury, making clear "this must not be seen as any kind of precedent."
Her comments were echoed by Rebecca Evans, her Welsh counterpart, who complained she had been forced to donate £30 million of money earmarked for "devolved areas, like health and education."
But the Treasury "strongly disagreed" with her characterisation of the request, saying government departments across Whitehall had also been asked to make a contribution through their underspend.
A spokesman denied that a precedent had been set for raiding devolved budgets for reserved spending areas, saying: "This is a response to an extraordinary crisis."
Simon Clarke, the Chief Secretary to the Treasury, asked the devolved administrations to make a contribution towards a £1 billion fund that will be used to provide state-of-the art equipment.
He said they could either hand over the cash from their budgets or accept a reduction in the Barnett formula funding they receive from their block grants from Westminster.
The request was highly unusual as foreign aid and defence spending are reserved to Westminster.
However, SNP ministers in Edinburgh have previously voluntarily spent money in other reserved areas such as international development by sending aid to other countries, including Ukraine.
They have provided £4 million for provide basic humanitarian assistance in health, water and sanitation, and shelter for those fleeing the war-torn country.
The Scottish Government said its £65 million would be used to help fund "sophisticated air defence systems and thousands of pieces of vital kit for Ukrainian soldiers."
'Funding these areas should be done by the UK government'
Ms Forbes said: "This further funding is to assist Ukrainian armed forces to fight Russian aggression and the unspeakable brutality being perpetrated.
“We have agreed to providing funding on this occasion given the clear need to maximise the international effort to support Ukraine. However, we are clear that this must not be seen as any kind of precedent which leads to devolved budgets being used to help pay for clearly reserved policy areas.”
Ms Evans said it was "right the UK should continue to provide much-needed military support and we will continue to provide humanitarian support to the many people from Ukraine who arrive in Wales every day".
But she added: "What is not right is using money that should be for investment in devolved areas, like health and education, to fund a non-devolved spending area - military aid and defence.
"We have accepted this outcome because of our ongoing commitment to support Ukrainian people and to avoid future budgetary uncertainty, but funding for these areas should rightly be met by the UK government."
Jeremy Miles, the Welsh Education Minister, told BBC Radio Wales that ministers "were told by the UK Treasury the budget would be cut" and "there wasn't any consultation."
David TC Davies, a Wales Office Minister, said: "At the end of the day, the parliamentary government is not going to do anything to undermine devolution."
