Mr Salmond addressed a gathering in Portlethen, Aberdeenshire, with Prime Minister David Cameron and his Cabinet just a few miles away on their own visit to the north east.
The two Cabinets' close proximity was a "wasted opportunity" to stage a public debate between the First Minister and Prime Minister, he said.
He described the Westminster Government's visit as a potential "portent" of his hopes for an independent Scotland.
He said: "If at any point David Cameron walks in, I am available for this debate.
"The UK Cabinet has come to Aberdeen but they're not going to have any public discussion or access.
"It does seem a wasted opportunity, not just for the First Minister and the Prime Minister to debate, but to have people from this area question the UK Cabinet over its range of responsibilities."
Mr Salmond welcomed the report by Sir Ian Wood, which recommended a new energy regulator to be based in the north east.
He said: "I've got some form in oil and gas as I was an energy economist before I fell among thieves, by which I mean the House of Commons and not the Scottish Parliament or the Scottish Government.
He added: "We are told today that North Sea oil and gas is better handled by a big country like Britain as opposed to a small country like Scotland.
"That's a very interesting concept for people in this part of the country, who can glance across the North Sea to Norway, a country smaller than Scotland but a country which by every observation has handled its oil and gas resources better than the stewardship of Westminster."
Mr Cameron toured a BP installation 150 miles east of Aberdeen ahead of a Cabinet meeting in the city yesterday afternoon, and argued that Scotland alone would find it harder to invest and deal with oil market volatility.
He said: "I profoundly believe the United Kingdom will be better off if we all stay together. We all bring things to this United Kingdom and I've been very clear to say on behalf of the rest of the United Kingdom to the people in Scotland we want you to stay.
"We think that we'll benefit by you being in the United Kingdom, by keeping this family together, but in the end the choice has to be for people in Scotland. It's their choice, they will make it, but I think it's important to lay out all the arguments of the benefits of staying together."