Just days after Barroso refused her request for talks on Scottish entry to Europe, the Deputy First Minister wrote to the foreign ministers of each EU state to promote the SNP Government's pro-European credentials, contrasting them with David Cameron's euro-scepticism and saying that the Nationalist Government did not support an in-out referendum on Europe.
Citing the Prime Minister's offer this week of an in/out referendum on Europe in 2017 under a future Tory government, Sturgeon said she wanted to reassure the other member states that "Scotland remains committed to the European Union".
Aimed at forging alliances which could ease future Scottish entry to the EU, the unprecedented move is also a bid by the SNP to regain the initiative on Europe, after a bad few months in which ministers had to admit EU entry would require detailed negotiations and would not be automatic, as they had claimed.
In her letter, Sturgeon said Scotland benefited "greatly from the peace and security provided by membership", noting the freedom of movement for EU citizens and the economic benefits of trade.
She said: "I therefore want to assure all Member States that following a positive result in the [independence] referendum we would work with the United Kingdom and the rest of the EU in partnership to ensure we continued to play an active part in that community of interest."
She said the SNP Government did want reform of "certain aspects of the EU", especially fishing, and would like to see more ambitious targets on carbon emissions.
"However, we understand that those reform ambitions can only be achieved through dialogue with Member States from within the EU.
"That is why we do not support the holding of an in/out referendum on the United Kingdom's membership. We have no intention of leaving the European Union. On the contrary, we will seek to be a constructive member of the Union working with other Member States to maximise the benefits we have enjoyed as members for over 40 years."
In her final paragraph, she said that if Cameron did hold a referendum in 2017, she hoped "by that time Scotland will be an independent Member State and will be playing its part as a valued and active partner within European Union".
Jackson Carlaw, the deputy leader of the Scottish Tories, said the letter was "yet more self-important posturing" from Sturgeon.
He said: "It is a breathtaking arrogance of an increasingly strident SNP leadership to assert that while the people of Scotland should be given a say on the break-up of the UK they should be denied any voice on our country's future relationship with Europe."
Sturgeon, like the First Minister, has always been pro-European.
However, recent polling suggests Scots are only marginally less Eurosceptic than those living south of the Border, suggesting the SNP's enthusiasm for Brussels could yet backfire.