Mr Salmond and Better Together leader Mr Darling will go head-to-head in the live debate on STV from 8pm to 10pm in what is billed as the first major set-piece between the figurehead from each camp.
Leaders of the Yes and No sides claimed the televised format with an audience would aid their campaigns and allow them to pin down their opponents on key issues about the referendum.
Better Together Campaign Director Blair McDougall said: “Voters in Scotland have been listening to the independence debate for over two years now. Surely, if Alex Salmond had convincing answers on the details of separation, we would have heard them by now.
“Scots tuning in deserve to finally get straight answers from Mr Salmond to the questions they have been asking. What would separation mean for our pound, pensions and public services?”
Yes Scotland chief executive Blair Jenkins suggested that Mr Salmond, who has also demanded a debate with David Cameron, was a more popular figure than politicians such as former Labour chancellor Mr Darling.
Mr Jenkins said: “Viewers will get the chance to hear why decisions made on Scotland’s future should be taken here in Scotland. Our experience is that most undecided voters choose Yes when they hear both sides of the debate, and therefore we believe the mass TV audience will benefit our positive campaign.
“We also believe that the No campaign have a problem with both the negativity of their message, and the unpopularity of their messengers.”