Ministers under Nicola Sturgeon have said their money should no longer be given to Ukraine for arms after being pressured by the Treasury to hand over £65million.
Scottish Finance Secretary Kate Forbes said the money would be provided “on this occasion”.
But she told the Treasury that the spending “should not be taken as some kind of precedent”.
Her Welsh counterpart Rebecca Evans echoed the remarks, complaining that she had been forced to donate £30million of money intended for “devolved areas, such as health and education”.
The Treasury hit back, saying they “strongly disagree” with his description of their request for financial support.
They added that government departments in Whitehall had also been asked to contribute through their underutilization.
The Treasury’s £1 billion fund for Ukraine will be used to produce state-of-the-art equipment.
Devolved administrations were given the option of contributing directly to the fund or taking a hit to their funding from Westminster via the Barnett formula.
A spokesperson denied that a precedent had been set for plundering decentralized budgets for earmarked spending areas, saying: “This is a response to an extraordinary crisis.”
The request made was highly unusual, as usually foreign aid and spending comes directly from Westminster.
However, SNP ministers in Edinburgh have already voluntarily spent money on other earmarked areas such as international development by sending aid to other countries including Ukraine.
For example, in the past they have provided £4million to provide basic humanitarian aid in health, water and sanitation, and shelter to those fleeing the beleaguered country. the war.
The Scottish government said its £65million contribution would be used to fund “sophisticated air defense systems and thousands of pieces of vital equipment for Ukrainian soldiers”.
The £bn of additional support brings the UK’s total military and economic contribution to Ukraine to £3.8bn.
Along with additional economic support for Ukraine, Boris Johnson today announced he would put 1,000 British troops on higher alert so they can be rapidly deployed in the face of Russian aggression.
Mr Johnson said: “Vladimir Putin’s brutality continues to claim Ukrainian casualties and threaten peace and security across Europe.
“As Putin fails to realize the gains he had anticipated and hoped for and the futility of this war becomes apparent to all, his attacks on the Ukrainian people are increasingly barbaric.
“UK weapons, equipment and training are transforming Ukraine’s defenses against this attack. And we will continue to stand firmly with the Ukrainian people to ensure Putin’s failure.
Ms Forbes said: “This additional funding is intended to help Ukraine’s armed forces fight against Russian aggression and the unspeakable brutality being perpetrated.
“We have agreed to provide funding on this occasion given the obvious need to maximize the international effort to support Ukraine. However, we are clear that this should not be seen as some sort of precedent leading to the use of decentralized budgets to help pay for clearly earmarked policy areas.
Ms Evans meanwhile agreed on the need for military support, adding “we will continue to provide humanitarian support to the many people from Ukraine arriving in Wales every day”.
But she added: “What’s not fair is using money that should be earmarked for investments in decentralized areas, like health and education, to fund an area of spending not decentralized – military aid and defence.
“We accepted this outcome because of our continued commitment to supporting the people of Ukraine and avoiding future budgetary uncertainties, but funding for these areas should rightly be borne by the UK government.”
It comes as Russian Foreign Minister Sergei Lavrov said a new “iron curtain” was coming down between Russia and the West.
Meanwhile, Oleksii Hromov, a brigadier general in the Ukrainian Armed Forces, revealed that Russia stepped up its missile strikes in the second half of June.
Mr Hromov told a press conference that more than half of the missiles came from Soviet reserves and were less accurate, adding that this was the reason Russia was hitting residential buildings, which Russia denied .
Earlier this week, Volodymyr Zelensky claimed that a shopping center with 1,000 people inside was hit by a Russian missile, killing 18 people inside. 36 other people are missing.