The former prime minister is among senior Labour figures being deployed in a final push by the party to prevent its supporters being won over by the Scottish National Party.
With polls suggesting a late swing towards the Yes camp, Mr Brown urged voters not to “abandon” the huge value to Scotland of pooling resources with the rest of the UK in areas such as pensions and healthcare.
The SNP does not give the same priority as Labour to social justice, he insisted, as part of a concerted fightback against nationalist attempts to move the argument on to traditional Labour territory.
“We wake in the morning thinking about how we can help people out of poverty and get people into jobs ... how we can build a better health service, better education services for our children,” he said.
“They wake up in the morning with one ambition: to break every single political link with the United Kingdom.”
He told an audience of activists and politicians at Westminster he had asked Speaker John Bercow to allow him to lead a debate when the Commons resumes business in October to galvanise cross-party support for reforms.
A pledge of extra tax and legal powers for Holyrood in the event of a rejection of independence in the popular vote has been signed by the leaders of all three main Westminster parties.
Mr Brown said the aim should be the “maximum local decision-making powers that is possible” while maintaining the union.
“The status quo is not now an option. A no vote does not mean no change. A no vote will usher in the further constitutional reforms in social, economic and fiscal affairs and a no vote will mean the choice you have made is against separation but for further devolution to the Scottish Parliament,” he said.
“Over the next few months after the referendum, we can take the lead in ensuring that these powers – that the Conservatives and Liberals say they would support – can be implemented as quickly as possible.
“I have asked the Speaker that when Parliament returns after the referendum in October, that in the first week he allows me to lead a debate about how we can secure the timetable and the delivery of the further devolution proposals.
“This is not like 1979 when the then-Conservative government promised change and then denied us it. This is like 1997 when the Labour government came in and, within a year, had delivered its promise of a Scottish parliament. When we are talking about the future of the constitution, London must and will change, Westminster must and will change, and, of course, the United Kingdom must and will change.”