He told listeners to a BBC Radio Scotland phone-in programme that he had been elected on a pledge to hold the historic vote, and would continue at the helm even if he fails to secure victory.
Mr Salmond was answering questions from voters for more than 90 minutes on a range of issues, from the taxation and currency arrangements in an independent Scotland, to the affordability of pensions and childcare.
Asked by one caller if he would resign immediately in the event of a No vote, he said: "No, I will discharge my responsibility. I was elected as First Minister in 2011, and I would like to serve out my term."
Mr Salmond also welcomed comments from Scottish Secretary Alistair Carmichael, when he was asked about the future of Scottish MPs in the event of a Yes vote.
Mr Carmichael has indicated he could step down from the UK Government and join Mr Salmond's ''Team Scotland'' to negotiate a deal on independence if Scotland says Yes.
"I was very much interested in the comments of Alistair Carmichael yesterday," Mr Salmond said.
"Scottish politicians have to be part of Team Scotland, and that was a very important and welcome statement from Alistair Carmichael."
Mr Salmond also addressed concerns that the referendum is proving divisive, with one voter raising the issue of anti-English feeling north of the border.
The First Minister said: "I absolutely believe that any residual anti-English sentiment in Scotland would disappear, because we would take responsibility for ourselves.
"When things go wrong in Scotland it would be our responsibility to sort them out as opposed to blaming someone else.
"We value, absolutely value English people in Scotland, they are part of the community."
Issues such as Trident and EU membership were also raised during the phone-in.
Trident, Mr Salmond said, was "a red line issue", and a pledge to remove it from Scotland would be non-negotiable.
He also repeated assertions that Scotland's EU membership would be "a smooth transition".