The Nationalists emphasised how the MP for Bromsgrove previously described devolution as "nothing short of constitutional vandalism" and claimed it was only "done to shore up support for Labour".
Angus Robertson, the SNP leader at Westminster, said: "Given his extreme hostility to the Scottish Parliament, the promotion of Sajid Javid is a clear sign that the Tories are not able to offer any kind of positive vision for further devolution.
"Mr Javid could not be clearer: he doesn't like any form of self-government for Scotland and he certainly won't be in favour of any more powers for Holyrood.
"How can the Tories possibly square his cynical comments with the promise to offer any kind of enhanced devolution if there is a No vote in September?"
He added: "It is all smoke and mirrors as Mr Javid's comments confirm; the Tories would block further constitutional progress for Scotland."
But the Secretary of State's Conservative colleague, David Mundell, the Scotland Office Minister, hit back, accusing the Nationalists of hypocrisy.
"They focus in on old comments from somebody about devolution when Nicola (Sturgeon) herself has said that the SNP don't support devolution."
The Tory MP stressed that the Coalition's record, "of which Sajid has been a part", was one of devolving significant powers to the Scottish Parliament.
Mr Javid, who only became an MP in 2010, has enjoyed a remarkable promotion through the ranks in just four years. He becomes the first Asian man to be a member of the UK Cabinet.
Prior to becoming an MP, the father of-four ran Deutsche Bank's trading operation in Asia, where he reportedly earned £3m a year and is said to have amassed £20m during his banking career, but turned to politics to "give something back".