Boris Johnson is calling on MPs to back his plan to hold an early general election on 15 October.
The PM has laid a motion in the Commons to secure the poll. To succeed, it needs the support of two-thirds of MPs.
But Labour, the SNP and the Liberal Democrats have said they will not vote in favour.
It comes after MPs backed a bill to block a no-deal Brexit if the PM hasn’t agreed a plan with the EU ahead of the 31 October deadline.
Mr Johnson dubbed it a “surrender bill” that would “cut his legs off” for negotiations on a new deal, minus the controversial backstop.
But the bill passed all its stages in the Commons in one day, with the support of most opposition parties and Tory rebels, as they tried to push it through ahead of Parliament being suspended next week.
It will now go to the Lords for approval.
Peers are debating a business motion on how to move forward with the bill on Thursday – but pro-Brexit peers have laid down over 100 amendments to derail its progress.
The PM warned on Tuesday that he would return to the Commons with a motion for an election under the Fixed Term Parliaments Act if the bill got to this stage.
Speaking as he introduced the motion, Mr Johnson said the bill approved to block a no-deal “hands control to Brussels”, and “scuppers any serious negotiations”.
He said it would force him to “surrender” to the EU, adding: “I refuse to do this and it is clear there is only one way forward for the country.
“In my view, and in the view of this government, there must now be an election on Tuesday 15 October.”
But Labour leader Jeremy Corbyn said Mr Johnson’s offer of an election was “a bit like an offer of an apple to Snow White from the Wicked Queen… offering the poison of a no deal”.
He added: “Let this bill [to block a no deal] pass and gain Royal Assent, then we will back an election so we do not crash out.”
The leader of the SNP in Westminster, Ian Blackford, said the debate about an early election was only going ahead because the PM had lost the vote against the bill.
He added: “[Mr Johnson] must accept the will of this House, accept the bill that Parliament has passed, accept your duty as prime minister and go to the European Council on 17 October and negotiate the extension you have been instructed to deliver.”
Leader of the Liberal Democrats, Jo Swinson, praised the cross-party work on the bill as “putting the national interest first”, but condemned Mr Johnson’s reaction.
“I am intrigued that as a result of this vote… the prime minister’s response is this somehow messes up his plan,” she added.
“If he is seriously saying the extent of his plan was to try to bully the EU and only get a good deal by threatening [to] leave without a deal… it is not very well thought through.”
But Tory MP Nigel Evans criticised the opposition, telling the Commons: “They have been given an opportunity [for an election] and they are running scared – not just from the prime minister, not just from a general election, but from the people of this country who in 2016 said they wanted to leave the EU.”
Earlier, shadow Brexit secretary Sir Keir Starmer told Labour MPs the leadership would not back an election until a Brexit delay had been agreed with the EU – making the 15 October proposal impossible.
But the First Minister of Scotland and leader of the SNP, Nicola Sturgeon, tweeted that the opposition parties must “seek to force [an] election” after the bill becomes law but before Parliament is suspended.
She added: “It’s starting to feel like Labour doesn’t want an election at all and leaving this PM in place knowing he’ll try every trick in book to get what he wants would be irresponsible.”
What does the no-deal bill say?
The bill says the prime minister will have until 19 October to either pass a deal in Parliament or get MPs to approve a no-deal Brexit.
Once this deadline has passed, he will have to request an extension to the UK’s departure date to 31 January 2020 – and, unusually, the bill actually includes the wording of the letter he would have to write.
If the EU responds by proposing a different date, the PM will have two days to accept that proposal. During that time, MPs – not the government – will have the opportunity to reject the EU’s date.
The bill also requires ministers to report to the House of Commons over the next few months. potentially providing more opportunities to take control of the timetable.
Be aware though, this could all change over the next few days because MPs and peers have the power to pass amendments to any law.
Meanwhile, the fallout from No 10’s decision to withdraw the party whip from 21 Tory rebels who backed the bill to block no deal has continued to face criticism from others in the party.
High profile figures, including two former chancellors and Sir Winston Churchill’s grandson, were expelled from the Parliamentary party on Tuesday night.
Now a group of around 80 Conservatives have written to the prime minister, calling on him to re-instate the whip to the “principled, hard-working and dedicated” MPs.
In a statement on behalf of the “One Nation Caucus”, former minister and Tory MP Damian Green: “Removing the whip from valued colleagues who have served their country and party with distinction damages our hope of winning the next general election.”