The head of the Better Together pro-UK campaign will also give his strongest indication yet he would support proposals for additional powers for the Scottish Parliament.
In a speech to the Convention of Scottish Local Authorities' annual conference in St Andrews, Mr Darling, the former Labour chancellor, say: "Scotland is not Holyrood.
"Surely this is a time to look at what councils do and what they are for.
"More and more power has been taken from local authorities and less and less attention paid to what people actually want to decide themselves.
"The world looks different from the Highlands and Islands and the north-east, or the Borders."
He added: "We have always known Whitehall does not know best. Neither does Holyrood. This debate should be about more than asking ourselves if we want to take power from one Parliament in London and give it all to Parliament in Edinburgh."
Mr Darling will also acknowledge Conservative and Liberal Democrat pledges to extend devolution of powers from Westminster to Holyrood if Scots reject independence in next year's referendum. He will tell delegates: "The Scottish Conservatives, with an enthusiasm that would have surprised many just a few years ago, have set themselves on a course towards further devolution.
"The Scottish Liberal Democrats have already published proposals for home rule within a federal United Kingdom.
"While my own party will set out the first findings of our devolution commission, looking not just at the constitutional powers, but the whole question of where power lies in Scottish society and how it can be more equally distributed.
"The point is, devolution is a process – but independence is a complete break and a one-way ticket to a deeply uncertain future."
Mr Darling's speech comes a day after Cosla president David O'Neill called for a large-scale decentalisation of power. In a veiled attack on the SNP Government, which has been accused of dictating policies to Scotland's 32 councils, he said centralisation was "the enemy of everything we stand for in local government".
The Centre for Scottish Public Policy think tank, in a pamphlet published in association with The Herald yesterday, also called for a debate on reshaping public services and the bodies that deliver them.
Scottish Labour is drawing up proposals to develop devolution. An interim report will be presented to the party's conference in Inverness next month. Final plans will be announced a year from now.
And MPs and MSPs are considering a range of possible extra powers for Holyrood and are understood to be keen on devolving some responsibilities down to local authority level.