The former SNP leader, who was First Minister when Megrahi was controversially freed from a Scottish jail, said the evidence used to convict him was “open to question”.
The claim was made by Mr Salmond on his television programme “The Alex Salmond Show”, broadcast on Kremlin-backed RT.
He was speaking after interviewing Kenny MacAskill, the Justice Secretary who announced the release of Megrahi in August 2009 having served eight and a half years of a life sentence.
Mr Salmond said: “As Kenny MacAskill has told us he made his decision to release Mr Megrahi according to the law of Scotland and on compassionate grounds.
“Here is my view: Is it possible for someone to be guilty, yet wrongly convicted? Yes it is.
“Kenny MacAskill was correct, the forensic evidence complied by the Scottish authorities and the FBI clearly identified Libyan involvement and Malta as the place where the bomb was planted.
“Mr Megrahi was a high ranking Libyan intelligence official on the scene at the time. This supports the charge that he, acting with others, was part of the Lockerbie conspiracy.
“However, his conviction was not just based on the strength of that evidence but on identification evidence which is to say the least open to question.
“Back in 2009 Kenny MacAskill was aware of this, as was I as Scotland’s First Minister. And we were aware of something else the total cynicism of some of those who attacked the Scottish Government for our decision.
Mr Salmond added: “Throughout this period the British government, of first Tony Blair and then Gordon Brown, were secretly acting to promote Mr Megrahi’s release. And not on the grounds of compassion or justice, but for trade, for big business and for oil. Such is State hypocrisy.”