The former SNP leader was speaking after the launch of his newly-formed Alba Party which will only contest regional list seats.
It comes after a turbulent period for the SNP and the Scottish Government, led by Mr Salmond's successor, Ms Sturgeon.
He told the Sunday Mail: "I believe that she should be the First Minister because the SNP should win a handsome majority.
"She is the only viable independence candidate and therefore she is the best one.
"I have no ambition to be in government. I am not standing to be First Minister, I am standing for the Alba Party on the list to build an independence super-majority."
Mr Salmond said his party will be carrying out a "positive" campaign and urged voters to back the SNP or another pro-independence party in the constituency seats.
The Alba Party will only be fielding candidates in the regional lists in an attempt to boost separatist numbers in Holyrood.
Ms Sturgeon told Scotland on Sunday: "The good thing about (Mr Salmond) now having his own party is I don't have to spend much time talking about him or thinking about him any more."
She added that she would have stood down if the result of the Hamilton Inquiry had been different.
"I would have tendered my resignation because I have always believed that the office of First Minister is bigger than any individual, and I would not have dragged the office of First Minister through the mud."
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