Plaid had offered £80m over two years for children with Additional Learning Needs
Welsh Labour's leader has said they will "be left with no choice" but to vote against the supplementary budget unless their demands are met.
As a minority government, Plaid Cymru must get the support of at least six Members of the Senedd (MSs) from other parties to pass the budget.
They had offered £80m over two years for children with Additional Learning Needs (ALN) in exchange for Labour support.
But Ken Skates, the interim leader of Welsh Labour, told BBC Politics Wales that the offer wold be a "bad deal for education".
He said: "If we don't get that fair deal for education, then I'm afraid it will leave us with no other option than to vote against the budget."
Speaking on behalf of the Welsh government Deputy Minister for Public and Preventative Health, Nerys Evans, accused Labour of "playing politics" with extra money for the NHS, childcare and free school meals.
She urged them to return to the negotiating table before the vote on Tuesday.
This supplementary budget is the allocation of extra funding for the Welsh government. The final budget was set by the previous Labour government before the election that was held in May.
Extra spending by the UK Labour government on ALN, known as SEND in England, means Welsh government has received a windfall.
That money is not ring-fenced for that purpose by the Welsh government, who can choose to spend it however they want, but Welsh Labour and other parties want to see more of it spent on ALN.
Plaid Cymru has offered £40m per year for two years to the sector and have promised to improve sustainability in the long-term.
Speaking on Politics Wales, Skates who is currently the only candidate standing in their leadership contest, confirmed they had rejected the offer on the table.
The ALN system was introduced in 2021 to replace the special educational needs system
He said Labour wanted £100m put towards ALN adding that it was "absolutely vital" that more money was put into education.
He added: "I believe that £40m this year is a bad deal for education, and I believe £40m next year would be another bad deal for education."
Skates said young people in Wales "deserve" an additional £100m set aside for education and specifically ALN.
Also appearing on the programme, Nerys Evans hit back and and accused Labour of "playing politics", adding "£80m for ALN is a lot more" than Labour's planned spending in the budget when they were in government.
She acknowledged that ALN needed "more investment" and said their plan to "surge capacity, look at options for early identification of ALN and look at training" was "sustainable".
The supplementary budget also included plans to spend £145m more on the NHS, £55m on childcare and £15m on free school meals.
Evans said the Labour Party has "spoken warm words" about supporting these policies in the past and urged the party to "look again" at the supplementary budget ahead of the vote.
The vote on the supplementary budget will take place in the Senedd on Tuesday.
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