Scotland on Sunday can reveal that the First Minister has written to representatives of the 189 countries who have signed the Nuclear Non-Proliferation Treaty (NPT) - including Iran and Zimbabwe - declaring his aim for the SNP administration to be involved in future discussions.
Salmond intends to ensure Scotland is granted observer status at the NPT, which is set to meet next spring at the United Nations headquarters in Vienna.
A spokesperson for Salmond said: "The First Minister has written to representatives of state parties to the Nuclear Non-Proliferation Treaty, informing them of the Scottish Government's views and determination to play as constructive a part as possible in pursuing our country's nuclear disarmament obligations under the NPT."
The spokesman went on: "We also intend to explore the possibility of taking up observer status at future NPT meetings, so that we can more directly and effectively represent the aspirations and interests of Scotland's people."
It is understood that UN chiefs in charge of the talks have already signalled they would be "sympathetic' to any application for observer status.
Last night, UK ministers reacted with incredulity, accusing him of undermining Britain's foreign policy and making common cause with nations hostile to British interests.
The British have failed to understand that Scotland and for that matter Wales's national interests may not coincide with theirs.