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Rushanara Ali said that she shared other MPs' revulsion at the "horrific and barbaric" actions of IS - also known as Isil or Isis - but was concerned that military action would create further bloodshed for the people of Iraq.
The Bethnal Green and Bow MP was appointed a frontbench spokeswoman on education last year, having previously served as shadow minister for international development.
In a letter to Mr Miliband ahead of the vote on Iraq, Ms Ali said:
"I understand the case that has been made and will not be voting against the motion. But I am unable in conscience to support the motion and I will make a deliberate abstention."
Labour MP Rushanara Ali has resigned from the party's front bench in order to abstain in the vote over military action in Iraq.
MPs backed Government plans to join air strikes against Islamic State in Iraq by 524 to 43, majority 481, after more than six hours of debate in an emergency recall of Parliament this afternoon.
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Bethnal Green MP has 'no confidence' that the potential impact on radicalisation in the UK has been properly thought through.