The MP for Norwich South, Clive Lewis, has said he quit the Shadow Cabinet with a "very heavy heart".
In his resignation letter to Jeremy Corbyn he said: "I know you understand the deep divide this issue has opened up in the country and it is to your credit that you have lead the debate in our party in such an open and comradely way."
Jeremy Corbyn has said he wishes Clive Lewis well and "looks forward to working with him in the future" after he resigned from the shadow cabinet.
Mr Corbyn has told Labour MPs to back the Brexit Bill at its third reading, something Mr Lewis said he could not do.
The Labour leader said: “I would like to thank Clive for his work in the shadow cabinet, which has underlined what an asset he is to the Labour Party and our movement.
“I understand the difficulties MPs representing constituencies which voted Remain have in relation to the European Union Withdrawal Bill. MPs have a duty to represent their constituents as well as their party.
“However, the Labour Party respects the outcome of the EU referendum, so we have asked all Labour MPs to vote for the Bill at its third reading tonight.
“We have been clear from the start that Labour will not frustrate the triggering of Article 50, which represents the start of the process for leaving the EU."
Clive Lewis posted this picture of Star Trek's Mr Spock.
It refers to the 'no win scenario' that cadets in the United Federation of Planets must go through before becoming officers.
Labour's Clive Lewis has resigned from the shadow cabinet in order to defy his party leader Jeremy Corbyn's three-line whip over the Government's Brexit Bill.
The shadow business secretary stepped down as he did not agree with the order to back the European Union (Notification of Withdrawal) Bill at its third reading.
He said in a statement: “When I became the MP for Norwich South, I promised my constituents I would be ‘Norwich’s voice in Westminster, not Westminster’s voice in Norwich’. I therefore cannot, in all good conscience, vote for something I believe will ultimately harm the city I have the honour to represent, love and call home.
“It is therefore with a heavy heart that I have decided to resign from the shadow cabinet.
“It has been a privilege to work with Jeremy Corbyn and be part of the shadow cabinet. I will continue to support our party and our leader from the back benches to the very best of my ability.”
Our Political Reporter Emma Hutchinson got some early reaction to Clive Lewis' decision to stand down.
In response to @labourlewis resignation Jeremy Corbyn says he wishes him well and looks forward to working with him in the future
Mr Lewis had pledged to vote against the bill if it went through unamended. The majority of his constituency voted to remain in the EU referendum.
Clive Lewis says "cannot vote for something I believe will ultimately harm the city I have the honour to represent, love and call home"
Norwich South MP and Shadow business secretary Clive Lewis and has resigned from the shadow cabinet in order to defy Labour leader Jeremy Corbyn's order to back the European Union (Notification of Withdrawal) Bill at third reading, its final Commons stage.
Our Political Correspondent Emma Hutchinson spoke with Daniel Zeichner about why he had decided to defy the whip and vote against the bill.Read the full story ›
A four-month-old baby was a first-hand witness to the vote on triggering Article 50 - coming along with his MP mother.Read the full story ›
A Conservative MP is to interrupt her maternity leave to vote for Article 50 and the beginning of the UK's move out of the EU.
Chloe Smith gave birth to her son in September and is due to return to work fully at the start of April.
Norwich North MP Ms Smith, alongside her husband Sandy McFadzean, plan to take the little boy into parliament next week so she can go through the voting lobbies.
The Norwich City Council area voted to remain while Broadland wanted to leave the EU. Both areas partly fall into Ms Smith's constituency.
She intends to vote in favour of the bill to invoke Article 50.
"Brexit is now the central issue of our times. I'll be there voting for this crucial bill to uphold the democratic result of the referendum.
"I'm grateful to everyone in north Norwich who's let me know their views."