East Sussex headteachers have billed the Treasury to the tune of £107,123,511.
The heads – along with more than 5,000 colleagues in 31 counties – sent invoices of varying amounts to the Chancellor Philip Hammond.
They said the bills represented the difference between the funding received by their schools and the amount received by schools in Westminster.
Brighton & Hove's invoice was for £48,133,230 and the West Sussex invoice was for £191,470,280.
As part of the FlatCashEd and WorthLess? campaigns, heads have spent more than two years fighting for fairer and more sufficient funding, but described their efforts with both the Treasury and the Department for Education as “constructive yet ultimately fruitless”.
In a letter to Mr Hammond, accompanying the invoice, they said: “Bluntly, it is neither sustainable nor credible for the Treasury and Department for Education to keep trotting out the same half-truths and partial information.
“We are fed up of being told that there is more money in education than ever before when parallel rising costs are completely ignored, or when the half a million extra children who have swelled our school rolls since 2010 seem to be entirely overlooked.
“Our schools need to be given the same ‘tools’ to deliver as other better-funded parts of the country.
“Our children all sit the same examinations and our schools are judged by the same Ofsted criteria.”
The headteachers have asked for a meeting with ministers from the Treasury and the Department for Education “to look at how these crucial issues can be resolved and to find a mutually acceptable way forward”.
Caroline Barlow, head of Heathfield Community College & Sixth-Form, said: "Any circumstance which drives headteachers into taking action in this way represents a serious professional concern for the well-being and life chances of our students.
"This is something our communities and parents understand all too well, as they are seeing the impact on their children of the choices many schools are having to take.
"It is disappointing to keep hearing a repeated rhetoric that bears no relation to the real-terms cuts to schools through rising costs, inflation and unfunded staffing costs.
"The additional funds found in September are a step in the right direction but do not account for the £3bn shortfall in school budgets by 2020.
"We look forward to continuing to work constructively with those who can make a difference to our young peoples education.”
The invoices were branded an "absurd stunt" and "not helpful" by one MP.
Sir Nicholas Soames added: "What makes for an asinine headline is not a serious way of getting money from the government.”