He told ITV’s Good Morning Britain the UK would pay what was legally due, “not just what the EU wants”.
Mr Davis said the UK treated its EU “rights and obligations” seriously but it had “not seen any number”, adding the EU was playing “rough and tough”.
The EU’s chief negotiator Michel Barnier is due to publish his guidelines for the talks later although they are not likely to include any financial demands.
An EU source has told the BBC that officials in Brussels will not enter into a discussion about potential figures for a final bill, likely to be one of the hardest-fought and most sensitive areas of the Brexit process.
Mr Davis said the negotiations had not started in earnest but indicated the UK would set down a marker when it came to talks over the divorce settlement.
“We are not supplicants,” he said. “This is a negotiation. They lay down what they want and we lay down what we want.”
Various figures had been knocking around, he said, but asked directly whether a figure of €100bn was acceptable, he replied: “We will not pay €100bn.”
He added: “We will do it properly. We will take our responsibilities seriously. What we’ve got to do is discuss in detail what the rights and obligations are.”
Many Conservative MPs argue the UK does not owe the EU anything given the size of the contributions it has made over the past 40 years. A recent report by a House of Lords committee argued the UK was not legally obliged to pay a penny although to do this would threaten any chance of a post-Brexit trade deal.
If the UK was to walk away without a deal, Mr Davis conceded that it would not owe anything but he insisted this was not the government’s objective.
“We want a deal. We think we can get a deal,” he told Radio 4’s Today. “We have said very very plainly we will respect our international obligations, our legal obligations, but they are not going to be determined for us.”
The EU has insisted that the UK will have to accept liabilities stemming from its membership, including contributions to the EU Budget. The EU has already listed some sort of agreement on a payment from the UK as a precondition for opening talks on a trade deal.
Previous calculations had placed the financial settlement likely to be demanded by the EU at between 50 and 60bn euros. The Financial Times, using the same economic model with new data from around Europe, suggests that has now gone up to 100bn euros.