The senior backbencher and Labour MP for Leeds Central is the author of the legislation put forward by a cross-party group which would require a delay to Brexit unless there was a deal or Parliament explicitly backed leaving the EU without one by October 19.
The snappily-titled European Union (Withdrawal) (No. 6) Bill 2019 also has the support of former Cabinet minsters Philip Hammond and David Gauke, a sign of how the rebel ranks have been bolstered following the change in Prime Minister.
Under the terms of the Bill, the Government must ask the European Union for a delay to Brexit until January 31, 2020 if no agreement has been reached and MPs have not agreed to a no-deal exit.
If the European Council proposes an extension to a different date then the Prime Minister must accept that extension within two days, unless the House of Commons rejects it.
Introducing the Bill, Mr Benn, who chairs the Brexit Select Committee, said: "I think wherever we stand on this issue, we know there is very little time left and, following the decision on prorogation, there is even less time than would have been available previously."
He added: "The purpose of the Bill is very simple. It is to ensure that the United Kingdom does not leave the European Union on October 31 without an agreement."
Mr Benn also said: "You could describe it as a somewhat unlikely alliance, but what unites us is a conviction that there is no mandate for no-deal, and that the consequences for the economy and for our country would be highly damaging."
He went on: "We must in my opinion secure that extension to Article 50 otherwise there is a risk that the election would result in us leaving without a deal, which as it may turn out at 7 o'clock tonight is not what the House of Commons wants and we should respect that."
During the debate in the Commons, Conservative MP Steve Double (St Austell and Newquay) called on Mr Benn to admit his Bill does not stop no-deal and instead extends the UK's exit from the EU.
Mr Double said: "Can we be clear - this Bill does not stop no-deal, it simply prolongues how long we take to leave. If you want to stop Brexit, revoke Article 50 and be honest with the country."
Following an intervention by SNP MP Angus MacNeil (Na h-Eileanan an Iar) who called for Article 50 to be revoked, Mr Benn said that he was against revocation.
He said: "Just as a no-deal Brexit is unacceptable, I believe revocation is not acceptable either."