The Commons voted by 329 votes to 302 - a majority of 27 - to approve an amendment brought by Tory ex-minister Sir Oliver Letwin allowing it to take control of business on Wednesday from the Government.
This will allow MPs to select their favorite Brexit option in so-called 'indicative votes', which are likely to include soft Brexit options and the possibility of remaining in the European Union.
Three ministers were among 29 Tory rebels who defied the Prime Minister and backed the amendment.
Minutes before the vote Watford's Richard Harrington quit as an energy minister in order to support the Letwin plan, accusing the Government of ‘playing roulette’ with people’s lives.
He was followed by Foreign Office minister Alistair Burt and health minister Steve Brine.
Theresa May indicated in the Commons earlier today that she would allocate Government time for indicative votes if the Letwin Amendment was defeated
Sir Oliver's move to give MPs control over the path to Brexit attracted cross-party support and won by a convincing margin in the Commons to heap fresh pressure on Theresa May
Energy minister Richard Harrington quit to vote for the rebel amendment, sending a letter to the Prime Minister accusing her Government of 'playing roulette' with people's lives
Earlier a group of eight Remainer ministers had reportedly indicated they would not vote for the amendment after meeting Mrs May.
Breaking the Tory whip to support it would have led to them having to resign their posts.
The Prime Minister had earlier told the Commons she would set aside Government time for votes if the amendment was defeated, in a bid to head off the rebellion.
Mrs May leaving the House of Commons tonight after addressing rebellious MPs who later voted to wrestle control of Brexit away from the Government despite her efforts to stop them
These are the seven options for Brexit MPs could vote on this week if Mrs May is forced towards a softer Brexit
She addressed the Commons this afternoon and admitted 'as things stand there is not sufficient support' to hold a fresh vote on her deal, quashing speculation that it would happen tomorrow.
She faces a move by rebel MPs who want to pass a motion in just a few minutes time to seize control of Brexit - giving them the power to hold a vote on Wednesday letting the Commons select its favorite Brexit option in so-called 'indicative votes'.
The PM vowed to whip against the motion proposed by Remainer rebel MP Oliver Letwin and also said she could ignore MPs' preferences if they try to force her to adopt a softer Brexit.
But she offered to hold indicative votes on government time in an effort to head-off the rebellion – meaning the votes would do ahead but rebel MPs would not be in control of the process.
WHAT WILL HAPPEN TO BREXIT THIS WEEK?
LIKELY TO HAPPEN WEDNESDAY: MPs HOLD INDICATIVE VOTES
The Commons is set to hold a series of indicative votes on Brexit alternatives this week, most likely on Wednesday. The alternatives include a softer Brexit, a second referendum or leaving with No Deal. If one commands a majority, MPs will try to pressure Theresa May into adopting that option. But there is no binding way of making her do so.
LIKELY TO HAPPEN BY THURSDAY: MAY HOLDS A THIRD MEANINGFUL VOTE ON HER BREXIT DEAL
May is likely to try and pass her Brexit deal a third time, after the EU offered a Brexit date of 22 May if she does so this week. The Prime Minister will use threats that MPs will take control and force a softer Brexit in an attempt to force Brexiteer rebels to finally back her. She may also offer them a date when she will quit in return for their support. Thursday is the most likely day for her vote, but there is a chance she won't hold it if she does not believe she'll win.
FRIDAY: MPs TAKE CONTROL?
If the PM loses a third vote on her deal, MPs and Remainer Cabinet ministers will try and force her towards a softer Brexit. Brexiteer MPs and Cabinet minister will conversely try and push her towards a No Deal exit from the EU. The most likely outcomes are:
Theresa May is under no obligation to accept MPs favoured option for Brexit, and could take Britain out the EU without a deal on 12 April. She could remain as Prime Minister under this option.
MPs could try and force May to negotiate a softer Brexit, but this will provoke outrage from Brexiteers. It does not necessarily mean a delay beyond a few months because Britain could still leave the EU under the withdrawal arrangement.
IF MPs vote for a second referendum either on May's deal or a range of options, it is likely to mean a lengthy delay to Brexit. May has indicated she will step down if Brexit is delayed beyond June 30.