The Shadow Defra Secretary Rachael Maskell has confirmed that she will step down from her position on the Labour front bench to vote against triggering Article 50.
Miss Maskell, an MP for York, said that the Government's plans for Brexit creates an "unjustifiable level of risk".
The announcement makes her the fourth shadow minister to reign over last nights vote, which has paved the way for Britain to leave the EU.
A number of other Labour frontbenchers also opposed the Bill, despite the leadership imposing a three-line whip.
Explaining her position, Ms Maskell said: "I have consulted with my constituents and local businesses throughout the process and held a number of meetings for them to voice their opinions.
"I believe that Theresa May’s Brexit ‘plan’ is creating an unjustifiable level of risk at a time of national and international uncertainty and volatility, with silence on national security measures, no mention of climate change mitigation or environmental protections, and no guarantee of good jobs or employment rights.
"The UK is no longer being offered a ‘people’s Brexit’ but a ‘Theresa May Brexit’, which goes far beyond just leaving the European Union, as voted on at the referendum last June."
It is not yet known who will be Corbyn's next pick for the Secretary of Department for Environment, Food & Rural Affairs.