With the deadline to register set for midnight on Tuesday, the First Minister will use a series of TV appearances to encourage people to play their part in a unique and historic vote on September 18.
He will also talk about the potential impact of independence on public services and the economy, the twin themes of the coming week. "People have been adding themselves to the electoral roll in record numbers," he said.
"Many will be voting for the first time in their lives. Those who never normally take part in elections - Scotland's missing million - are to play a decisive part in our nation's decision on 18 September."
As part of the push on registration, Yes campaigners began staging more than 200 weekend events across Scotland yesterday, including a "take over" of Glasgow city centre by the Radical Independence Campaign.
Better Together also said it was working "flat out" to encourage voter registration so people could reject independence. However No campaign insiders admitted their chief concern was "differential turnout", with highly motivated Yes supporters certain to vote, and No supporters more likely to assume the Union was safe, and stay home. With the No campaign's poll lead eroding, and the Yes camp buoyed by Salmond's victory over Alistair Darling in last week's TV debate, David Cameron yesterday told a newspaper he was feeling "nervous" about the referendum.
The Prime Minister said: "I'm emotional and nervous because it matters so much." Cameron said he believed a "silent majority" of electors would help maintain the Union.
Salmond added: "David Cameron says he is nervous about the referendum result, and he is right to be so, because people across Scotland are about to speak as they have never spoken before. For far too long, far too many people have felt excluded and disenfranchised by the political process, and their voices have not been heard - but the missing million are poised to speak, and when they do it will make the Hampden roar seem like nothing."
The First Minister also claimed there was a "jobs gap" in the Unionist offer of more powers for Holyrood in the event of a No vote.
"Independence isn't a magic wand but we'll be able to tailor economic policy to put job creation in Scotland first instead of a Westminster policy which has consistently favoured London," he said.
UK Labour leader Ed Miliband is due to return to Scotland this week to argue independence would threaten funding for public services.
Some trade unions registered as official No campaigners, such as the GMB and Usdaw, are also expected to raise their voices. Shadow Scottish Secretary Margaret Curran said Labour would focus on "bread and butter issues" such as jobs, wages, pensions and currency. Curran also said that if she were Scottish Secretary in a new Labour government she would give a guarantee of more powers.
"I would stake my reputation on delivering a devolution programme" for Holyrood, she said.
Sir Paul McCartney yesterday became the latest celebrity to come out in favour of a No vote, signing an open letter organised by the Let's Stay Together campaign. The declaration, which has so far attracted 50,000 signatures, states: "We want to let you know how very much we value our bonds of citizenship with you, and to express our hope that you will vote to renew them. What unites us is much greater than what divides us. Let's stay together."
Other signatories include Sir Mick Jagger, Sir Bruce Forsyth and Professor Stephen Hawking.
The intervention by the former Beatle provoked a slew of strained jokes. Labour MP for Stirling Anne McGuire said: "We are glad to have the Help! of Sir Paul McCartney. It is hardly surprising that Sir Paul wants us to Come Together. Maybe rather than trying to take us all on a Magical Mystery Tour, Alex Salmond should just Let it Be."
Yes Scotland said: "It's fantastic that Sir Paul loves Scotland, and we're sure he will continue to do so after Scots say 'Yeah, yeah, yeah'. The Westminster system belongs to Yesterday."
William Hill have shortened the odds on independence after a surge in bets for Yes. Before last week's TV debate, the bookmaker was quoting 5/1 for Yes, with No the 1/9 favourite. But spokesman Graham Sharpe said that after the debate "one-way traffic" had seen the odds tighten to 7/2 for Yes and 1/5 for No.