Councillor Chris McEleny resigned from the SNP just hours before he was revealed to be standing for the Alba Party on the west of Scotland regional list in May’s Holyrood elections.
Along with Mr Salmond, who is standing on the north east list, he joins Eva Comrie, who was the SNP list candidate in mid Scotland and Fife, but is now standing for Alba, and Cynthia Guthrie, who is standing in the south of Scotland.
The party aims to have four candidates on each of the eight parliamentary regional lists.
Mr McEleny said more names would be announced before the deadline of Wednesday.
Despite rumours of other high profile defections, The Scotsman understands Salmond ally Joanna Cherry MP, who is taking time off for health reasons, is not quitting the SNP.
In a tweet posted on Friday, Ms Cherry said: “Yesterday I said I was taking some time out for health reasons. Any speculation to the contrary is incorrect.
"I intend to return to work as the SNP MP for Edinburgh South West when I am able. Thanks for all the good wishes.”
Mr McEleny, who is a regular contributor to a controversial pro-independence blog, has criticised Nicola Sturgeon for failing to have a Plan B on delivering a second independence referendum and for the party’s attempt to reform the Gender Recognition Act.
Speaking after Ms Salmond launched his new party, Mr McEleny said he believed the only way to secure indyref2 was by having a “super-majority” in the Scottish Parliament, which could not be ignored by Prime Minister Boris Johnson.
He also said more pro-independence parties in Holyrood would “take the pressure off the SNP” in terms of the “groundwork on the independence offer”, allowing it as the party of government to “get on with the day job”.
“This is a huge opportunity to really drive for independence,” he said.
“The SNP failed to get a majority at the last election. They may get one this time, but we need more pro-independence MSPs than just the SNP to really make a difference.
"Of course it was a huge decision to leave the party. I joined just after Alex Salmond convinced Jimmy Reid to join the SNP and I’ve been the SNP group leader on the council, so it was a wrench as I have a lot of love for it.
"I still want people to vote SNP in their constituencies. This is not about undermining the SNP, but adding to the pro-independence movement.”
Asked if he was concerned about the allegations which had been made against Mr Salmond about his behaviour towards women, he said: “Alex Salmond has been cleared by a court and been through two inquiries. He’s a man of integrity and inspirational to so many.”
With Scottish Greens, Independence for Scotland and the Alliance for Independence also standing on regional lists, Mr McEleny said he was unconcerned another party would split the vote, and the smaller parties may join forces with Alba.