The UK will refuse to hand Brussels £50 billion to pay for its divorce from the European Union, David Davis has insisted.
When Theresa May triggers Article 50 on Wednesday, starting the two-year countdown to Brexit, the demands for cash will form one of the first stumbling blocks in the negotiations.
Mr Davis said the UK would meet its obligations - but he did not expect to see "that sort of money change hands".
When talks begin after Mrs May sends her Article 50 letter to European Council president Donald Tusk this week, EU chiefs are expected to seek an early agreement on an exit fee - meant to cover the UK's outstanding liabilities such as pensions and projects it has already pledged cash to.
European Commission president Jean-Claude Juncker has confirmed he expects the UK's "divorce bill" for Brexit will be around £50 billion.
But on a BBC Question Time Brexit special, Mr Davis said: "The Prime Minister said we are coming to the end of the time when we are paying enormous sums to the EU.
"We will, of course, meet our international obligations but we expect also our rights to be respected too.
"I don't think we are going to be seeing that sort of money change hands."
Mr Davis also insisted:
:: There are contingency plans in place in case the UK failed to secure a deal on future trading arrangements with the EU but stressed a "comprehensive" agreement remained the Government's goal
:: He is right to set "ambitious" aims for the negotiation strategy
:: Immigration policy would be set by the UK in the "national interest" - meaning that "from time to time" the numbers of people coming to Britain could increase.
The Brexit Secretary's appearance on the special edition of the BBC show came after Mrs May and Scotland's First Minister Nicola Sturgeon clashed over the SNP leader's demand for a second independence referendum.
The First Minister wants to hold another vote on leaving the UK between autumn 2018 and spring 2019, a timescale the Prime Minister is set to reject.
Mrs May has said a referendum during that period would be "unfair" to voters because they would not have all the necessary information to make a choice.
But following a meeting in Glasgow, Ms Sturgeon insisted the Prime Minister had been clear the terms of the UK's divorce from the EU and the details of a new free trade deal would be known within two years.
Ms Sturgeon said it was "very difficult" for the Prime Minister to maintain a "rational opposition" to a referendum on her timetable.
Ms Sturgeon said: "When I put it to her that what she was suggesting was that in a period of 18 months to two years from now, the terms of the future relationship of the UK and the EU would be clear, she said yes that is what she was saying."
But Mrs May, who used the visit to claim that the four nations of the UK were an "unstoppable force" when they worked together, told reporters her position will not change on Ms Sturgeon's call for a referendum by spring 2019.
The Prime Minister said: ''Now is the time when we should be pulling together, not hanging apart. Pulling together to make sure we get the best possible deal for the whole of the UK.
''Also I think it would be unfair on the people of Scotland to ask them to make a significant decision until all the facts were known, at a point where nobody knows what the situation is going to be."
Mr Davis insisted the Government remained committed to striking a comprehensive free-trade agreement with the EU but a "no deal" situation would not be as bad as critics claimed.
He dismissed EU negotiator Michel Barnier's warnings the UK would not be able to import nuclear fuel and would face queues of lorries at Dover as trade ground to a halt because of the increased bureaucracy.
"We have got a huge contingency plan exercised across all of these issues, every department of government," he said.
He acknowledged "no deal is not as easy as some would have you believe" but it would be "a lot better" than critics had claimed.
Mr Davis was challenged about his desire for a trade deal that will provide the "exact same benefits" as membership of the single market and customs union.
"One of the problems that happens when democracies negotiate is that the politicians are afraid of raising expectations," he said.
"The truth is we are negotiating for the future of our country.
"Therefore we want to raise the expectations as much as we possibly can, we want to aim as high as we possibly can.
"I make no apology for being ambitious about what we achieve."