The nomination of the former prime minister of tiny Luxembourg to be the next president of the European Commission signals the demise of Better Together's argument that big states wield all the influence in the EU, Salmond said.
Salmond said Juncker will be "an improvement" on previous president Jose Manuel Barroso, who argued that it may be "impossible" for an independent Scotland to join the EU.
The SNP has already welcomed Juncker's "sensible" statements on Scottish independence, when he suggested that the EU should keep out of the debate.
Meanwhile, the Tories have accused European leaders of "cowardice" for backing Juncker's appointment to the EU's top job. Health Secretary Jeremy Hunt attacked premiers for saying they would oppose his nomination in private only to support him publicly.
David Cameron conceded that he faces a tougher fight to persuade Britons to vote to stay in the EU after he was overwhelmingly defeated in his bid to block Juncker from becoming the next president of the Commission.
Nigel Farage said the defeat showed Cameron will not be able to renegotiate Britain's relationship with Brussels and claimed EU leaders would rather see the UK leave than thrash out a substantial new deal.
Farage insisted German chancellor Angela Merkel (pictured above) "wasn't for a moment" suggesting that Britain could opt out of ever closer union. "The result is to show David Cameron is friendless in Brussels, but ultimately, it's whatever Chancellor Merkel decides," he said.
Salmond added: "Mr Cameron has been pretty well humiliated. I cannot imagine why he made such an issue out of this. Nobody knew who Jean-Claude Juncker was before David Cameron started elevating him to some great bête noire."