The Scottish Government yesterday stressed the five-day visit as a trade mission and said the First Minister would be announcing hundreds of new jobs during his stay.
However a spokeswoman confirmed he would "reference" the referendum debate in a series of engagements during the visit.
The First Minister is due to speak at an event organised by Edinburgh Napier University today and will deliver the inaugural Caledonian Lecture at Glasgow Caledonian University's new New York City campus on Monday on "Scotland's place in the world".
He is also due to take part in a live interview and Q&A session with the Wall Street Journal and make a keynote address at the annual Bloomberg Energy Investment Summit during his trip, which coincides with US's annual Scotland Week celebrations.
The First Minister said the visit, organised by Scottish Development International, part of economic development agency Scottish Enterprise, would boost trade links.
He said: "The US is the largest inward investor into Scotland, therefore it is vitally important that we continue to build on this lucrative business relationship.
"The Scotland Week trade mission will capitalise on the increasing appetite for premium Scottish products across fashion, interiors and food and drink, which have a strong appeal with the American consumer."
He added: "I am confident that there will be a huge appetite for Scottish product in the Big Apple."
But the visit was criticised by Labour MSP Paul Martin.
He said: "The First Minister needs to explain why he thinks he can use taxpayer's money to go to the USA and lecture Americans on Scottish independence.
"Mind you, since he hasn't yet explained how he spent taxpayers' money on himself on a trip to the Ryder Cup in 2012, I don't think anyone should hold their breath for an answer.
"Alex Salmond uses taxpayers' cash as if it was his own."
His comments followed angry clashes at First Minister's Questions when Scots Labour leader Johann Lamont demanded answers about the cost of Mr Salmond's visit to the Ryder Cup golf tournament in 2012.
The First Minister stayed in the upmarket Peninsula Hotel in Chicago where suites cost more than £1,200 per night.
The Scottish Government has refused a request, made under Freedom of Information laws, for certain costs connected with the visit, though an appeal against the decision has been lodged.
Ms Lamont told MSPs: "I hope he's left the taxpayers' credit card behind because he still hasn't accounted for his spending on his trip to the Ryder Cup in 2012,
"The First Minister spent £500,000 to go to the Ryder Cup but he cannot or will not explain what he spent on himself."
Deputy First Minister Nicola Sturgeon - standing in for Mr Salmond as he travelled to the States - said: "I am quite flabbergasted that this is in the mind of Johann Lamont as the big issue of the day. All of the relevant information about the trip that Johann Lamont is, as far as I'm aware, in the public domain.
"If there are specific pieces of information that Johann Lamont wants then she can request them and I will undertake to seek to respond to that.
"It is right for this First Minister, as it was right for his predecessors, to go overseas to promote the economic interests of Scotland."