His top team will meet in Glasgow on Friday and Mr Miliband plans to host a public meeting in the area, mainly aimed at persuading undecided voters.
Senior Labour MPs will tour the country over Thursday and Friday.
It is being billed as a "big week" for Labour as polls suggest a rise in support for independence and a drop in support for the Better Together campaign.
Shadow Scottish secretary Margaret Curran said: "On Friday, I'll be pleased to welcome my shadow cabinet colleagues to Glasgow where we'll be discussing the issues that matter most to people across Scotland. We'll show that it's only Labour that has the positive, progressive vision to take Scotland forward."
The referendum, being held on September 18, is not being fought against a "Conservative England", she said.
"On Friday, Scots will see a Labour shadow cabinet made up of men and women from all across the UK, working in the interests of people the length and breadth of our country," she added.
"This week we will be saying loud and clear that the best prospects for a stronger Scotland lie with Scotland remaining part of the United Kingdom."
Labour MP Gordon Brown, the former prime minister, will also make an appearance in Glasgow on Tuesday to focus on pensions in a pro-union speech.
SNP MSP Annabelle Ewing said: "Sending more Westminster politicians on a day trip to help the Tory-led No campaign can only backfire, because the people of Scotland have heard it all before.
"They know full well that to ensure we get the powers we need to create a wealthier, fairer country and rid ourselves of the Bedroom Tax, Trident nuclear weapons and governments we don't vote for, Scotland needs to vote Yes in September."