Alex Salmond said the team will begin talks with the UK Government before the end of September, "marking the point at which the real negotiations will begin".
He said a number of people outside party politics have already been approached to take part.
The announcement comes as Labour said it will invite the SNP to work with it to make devolution work if Scotland votes No.
Mr Salmond revealed details of the so-called Team Scotland ahead of a speech in Inverurie in his Aberdeenshire East constituency to mark the 15th anniversary of the reconvening of the Scottish Parliament.
He said: "The independence opportunity gives the Scottish Parliament the chance not just to entrench the gains of the last 15 years but to raise our game to match the best.
"We should raise our sights and now look for comparisons not against the UK average but in light of the best in Europe. We should look to achieving Scandinavian levels of childcare, the Norwegian husbanding of natural resources and the German system of apprenticeships.
"That is the independence agenda of social and economic advance for the next 15 years which will inspire the people."
Commenting on the negotiating team, he said: "The independence team will secure expertise from across the political spectrum and beyond, and from Scotland and beyond, to begin talks with Westminster before the end of this September - marking the point at which the real negotiations will begin.
"I understand that people on the other side of the political debate cannot accept that at the moment, but hope and expect that they will be fully part of the Team Scotland approach once the votes have been cast. It is also the case that a number of people outside party politics - but with key expertise - have already been approached and the response has been universally positive.
"More clearly than anything else this demonstrates the wish of those of us on the Yes side to move forward in a consensual way once the people have spoken."
He added: "A mere 15 years after the reconvening of our Parliament we are currently engaged in the most exciting debate in Scottish democratic history with unparalleled levels of public engagement and participation.
"Part of the process of politicians rising to the challenge of the people is to commit to continue the mood of engagement after the result. The Team Scotland approach is part of that commitment."
Labour's shadow foreign secretary Douglas Alexander said it will be important to ensure Scotland does not ''divide more deeply'' after the vote on September 18.
In a speech in Edinburgh to mark the 20th anniversary of the death of Labour leader John Smith and the 15th anniversary of the first sitting of the Scottish Parliament, he will call for a ''politics of opponents, not enemies'' inspired by Mr Smith's example, and a ''respectful discourse of political discourse'' rather than a politics that ''descends into personal destruction''.
Meanwhile, in a tribute to Mr Smith, Labour's shadow Scottish Secretary Margaret Curran said: "After the referendum, regardless of the result, we have to come together and redouble our efforts to address the scourges of unemployment, poverty and inequality that John Smith dedicated his life to solving."