"I can not in good conscience support the terms proposed for our deal with the EU", Dominic Raab said on Thursday morning indicating that there is an ongoing dispute within the UK Cabinet about the Brexit deal.
May had been preparing to sell her Brexit deal to parliament, boosted by news that Europe is preparing a rapid summit to sign off on the agreement.
British Prime Minister Theresa May battled to save her draft Brexit deal Thursday.
The developments threaten to derail the prime minister's Brexit strategy ahead of a crucial EU summit, which European Council President Donald Tusk confirmed would take place on November 25, "if nothing extraordinary happens".
It was always going to be a challenge, but it's hard to imagine how Prime Minister Theresa May can recover from the biggest blow so far: the resignation of Dominic Raab, her chief negotiator and the minister responsible for Brexit.
Main opposition Labour Party leader Jeremy Corbyn said May should withdraw the "half-baked" Brexit deal and that Parliament "cannot and will not accept a false choice between this deal and no deal".
In a defiant statement at 10 Downing Street, May said her Brexit deal - which has attracted intense criticism from all sides - was in the national interest and made it clear that she had no intention of stepping aside.
Corbyn has said Labour will vote against any deal that does not meet its tests, which include delivering the same benefits Britain now has as a member of the EU customs union and single market.
"This is not the deal the country was promised", Corbyn stated in his floor speech, "and Parliament can not and I believe will not accept a false choice between this bad deal and no deal".
Work and Pensions Secretary Esther McVey and junior Brexit minister Suella Braverman have also quit, as have Anne-Marie Trevelyan, a ministerial aide at the education department, and Ranil Jayawardena, a ministerial aide at the justice department.
And leading backbench Brexiteer Jacob Rees-Mogg submitted a letter of no confidence in Mrs May to Sir Graham Brady, chairman of the Tories' backbench 1922 Committee.
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"This is not the deal the country was promised", he said.
May has vowed to fight on to the next election in 2022, but if enough lawmakers demand her resignation she will face a confidence vote.
But this bit is controversial - Brexiteers do not like the prospect of being tied to European Union customs rules, and Northern Ireland's Democratic Unionist Party has said it will not tolerate anything that creates a new border down the Irish Sea.
Rees-Moog told the press that Boris Johnson or former Brexit secretary David Davis - both of whom already resigned from the government earlier this year - would be better choices as prime minister.
Amid the political turmoil, the pound plunged on currency markets, falling 1.7 percent to $1.27, its second biggest drop after it fell 1.73 percent against the United States dollar in September.
In his resignation letter, Raab told May that it would give the European Union a "veto over our ability to exit".
Ireland's Government said it would not countenance a return to a hard border on the Emerald Isle under any circumstances, but a no-deal Brexit might very well make that unavoidable.
Thursday's mayhem pro- mpted a big fall in the pou- nd's value as investors fretted that United Kingdom could crash out of the European Union in March without a deal.
Corbyn added: "After two years of bungled negotiations, the government has produced a botched deal that breaches the prime minister's own red lines and does not meet our six tests".
Popular tabloid The Daily Mail carried the front-page headline "Judgment Day", urging its centre-right readership to give the deal "a fair chance".
An EU official warned that Britain was unlikely to get a better deal.