However, Better Together leader Alistair Darling said "there is no way back" from independence and his campaign would target undecided voters.
The latest opinion polls have suggested the vote is too close to call.
Both men were speaking to the BBC's Andrew Marr show.
Mr Salmond said: "We're not aiming to win by one vote. We're aiming to achieve a substantial majority if we can."
He added: "We tend to take the attitude that there isn't so much as a 'No' voter in Scotland, there are only deferred 'Yeses', and that's been one of the successes of our campaign."
Asked if he would seek another referendum if there was a "No" vote on Thursday, the SNP leader said: "If you remember that previous constitutional referendum in Scotland - there was one in 1979 and then the next one was 1997.
"That's what I mean by a political generation.
"In my opinion, and it is just my opinion, this is a once in a generation opportunity for Scotland."
Mr Darling commented: "I said a year ago that this race would narrow as we got towards the wire and that is precisely what has happened.
"It's not surprising. It's the biggest single decision we will ever take.
"If we vote to leave the UK on Thursday then there's no going back. It's not like an election where you can change your mind if things don't work out.
"If things go wrong this time, we've already voted - we're leaving.
"There is no way back, which is why in the next five days we will be targeting the 500,000 or so voters who have still got to make their minds up, because the decision is that critical."
He argued there was uncertainty over whether firms would move their headquarters out of Scotland and over how the NHS and pensions would be funded if the country became independent.
And he argued that "about a million jobs here in Scotland depend on us being part of the UK".
Mr Salmond told the Andrew Marr programme that if "Yes" won there would "cease to be a 'Yes' campaign and a 'No' campaign - there will be a Team Scotland".
He said he wanted "as many voices as possible" and welcomed an indication from Secretary of State for Scotland Alistair Carmichael last month that he would join such a negotiating team.
Mr Salmond said his negotiating team had "recruited specialism in a variety of fields".
The first minister renewed his claim that the Bank of England would be "a shared central bank" after independence.
"There will be a sustainability agreement between the governments in terms of borrowing levels and debt levels," he said.
"We set that out in our proposals."
The UK government has said it would not agree to a currency union with an independent Scotland, but Mr Salmond argued American economist Joseph Stiglitz had said "a shared currency is a very, very viable and common sense thing to do".
Meanwhile, Mr Darling again said the pro-Union parties would deliver more powers for the Scottish Parliament if there was a "No" vote.
"It's quite a clear choice now," he said.
"We can have faster, safer and better change, reform so that we can strengthen the health service, we can safeguard jobs.
"But you don't have the risks that come with independence, to jobs, to the funding of pensions and the health service, the uncertainty about currency."
Pressed on whether details of more powers would be available ahead of the vote, the Better Together leader said: "What has been agreed is the timetable that will bring together the proposals made by the three non-nationalist parties.
"Now that's abundantly clear that we will be able to start that process on Friday, if we vote to stay in the United Kingdom."
The interviews came after Yes Scotland campaigners claimed their private canvassing showed "the votes are there for a 'Yes' majority".
However, Better Together said the "No" vote was "holding up".
Three polls have put the "No" campaign in the lead, while one has put the pro-independence "Yes" campaign ahead.
The latest poll of polls collating the six most recent surveys - carried out between 9 and 12 September and excluding "don't knows" - puts the "No" campaign on 51% and the "Yes" campaign on 49%.
The pro-independence Yes Scotland campaign has not revealed the number of people it has talked to during its private canvassing, but claimed to have achieved a higher return than ever before.
Better Together campaign director Blair McDougall said polls showed the referendum vote was "on a knife-edge".
Better Together published a poll on Saturday suggesting 53.5% opposed independence and 46.5% backed it, when undecided voters were excluded.
The telephone poll, commissioned by Better Together from pollsters Survation, reached 1,044 respondents, with an effective sample size of 927.
Conducted between 10 and 12 September, it also pointed to a very high turnout, with 93% of voters surveyed saying they are certain to vote.
Another poll for the Observer newspaper, gave the "No" campaign a six point lead - 53% to the pro-independence campaign's 47%.
And a new Sunday Times poll - conducted by Panelbase - puts the voters who intended to vote "No" on 50.6% while the "Yes" campaign was on 49.4%.
However, an ICM poll for the Sunday Telegraph has suggested Scotland could become independent, putting the "Yes" camp in the lead. Excluding undecided voters it found "Yes" to be on 54% and "No" on 46%.
The poll was carried out between 10 and 12 September and had a sample size of 705 - smaller than many of the other polls.
A referendum on whether Scotland should become independent is to take place
Meanwhile, a leading economist has said there is "little basis" for "fear-mongering" over the economy of an independent Scotland.
Joseph Stiglitz countered the view of fellow Nobel prize-winning economist Paul Krugman, who recently warned that Scotland would face "huge risks" going it alone and told Scots to "be very afraid".
Mr Stiglitz said that while there would be risks in the event of a Yes vote, the risks of Scotland remaining in the union and UK leaving the EU would be "significantly greater".
In an article published in the Sunday Herald and the Scotsman, he urged Scots to focus on "vision and values" in the last few days before the crucial vote.
He said: "Krugman, for instance, suggests that there are significant economies of scale: a small economy is likely, he seems to suggest, not to do well.
"But an independent Scotland will still be part of Europe, and the great success of the EU is the creation of a large economic zone.
"By an order of magnitude, far more important than size is the pursuit of the right policies."
Scotland's First Minister Alex Salmond said the independence referendum was "a once in a generation opportunity" and he was aiming for "a substantial majority".