In an appearance at Edinburgh Book Festival in conversation with historian Sir Tom Devine, the First Minister said: "People say and do things in a campaign because they want an outcome, on both sides, but once the votes are counted you get into an entirely different situation. People then have to sit down and do what's best for the people of Scotland and the rest of the United Kingdom."
The First Minister also predicted a referendum day turnout of more than 80 per cent, citing unprecedented interest across the country during the campaign.
Mr Salmond said: "I think the best bet of this referendum is a bet on an 80 per cent poll. If you can get odds on an 80 per cent poll, you bet it."
Sir Tom agreed, saying: "It will be the biggest poll in Scotland's history in terms of turnout."
Mr Salmond added: "Absolutely, and many of the people who will be voting will be people who are not touched by opinion polls and opinion surveys, which tend to discount people with no voting record, and I think that's going to be a major factor."
The political exchanges between the two, billed as a conversation between the country's pre-eminent historian and a politician who once flirted with becoming a historian, delighted a packed audience and sparked off anecdotes.
One saw the First Minister recall his own family background, with a Tory mother who adored Winston Churchill and a hostile father. Mr Salmond recalled an interview which prompted headlines that his father wanted Churchill hanged. His father had responded: "What I said was that hingin' was too good for him."
Pressed on the RBS bail-out and what that would have done to an independent Scotland, Mr Salmond, a former economist at the bank, stressed that the part of the group which was behind the failure was its capital markets division based in London and under UK regulation.