Tony Banks, the head of a care home company which employs more than 1,000 people, will be a member of the Business for Scotland board.
Mr Banks - who featured in the Channel 4 programme Secret Millionaire - is one of around 350 businessmen and women from across the country who have joined the group.
Most members of Business for Scotland are involved in small and medium sized enterprises (SMEs).
Mr Banks, who fought in the Falklands with the Parachute Regiment and is now head of the Balhousie Care Group which has 27 care homes, argued that Westminster rule "simply isn't working for Scotland".
Business for Scotland will campaign in the run-up to next year's vote on the country's future.
Mr Banks said: "The SME community has a vital role to play in the referendum campaign because we help create jobs and generate wealth that can make Scotland the kind of country we know it could and should be.
"It is very clear Westminster simply isn't working for Scotland, or the rest of the UK. But a Yes vote next year will give us a once-in-a-generation opportunity to end the inertia, make our own decisions, realise our huge potential and rebalance the economy of these isles.
"That is good news not only for Scotland but for the rest of the UK too."
Independence could help achieve a major rebalancing of the UK economy, meaning that "in the long term, we will all be better", he said.
"In my view, a successful, vibrant and prosperous business community is a prerequisite to creating a better and fairer Scotland for everybody."
Business for Scotland declares that if the country leaves the UK, it "will become one of the wealthiest and most progressive nations in the world".
Some of the group's latest members are Ken Cairnduff who owns Cairnduff Developments and is founder of the Internacionale and Au Naturale stores; Ricky Nicol, chief executive and founder of telecoms company Commsworld; Michelle Thomson, an Edinburgh-based property entrepreneur; and Alan Knight, a documentary filmmaker from the capital.
Gordon Macintyre-Kemp, one of the founders of the new group, said: "We believe that a Yes vote will act as a catalyst for Scottish people to become more entrepreneurial, confident, successful, ambitious and international in their outlook.
"Our goal is to ensure that the Scottish SME business community has access to the facts and educated opinions that will allow them to make informed decisions in the lead up to referendum next year.
"We believe that when people take the time to investigate the facts it will be clear that Scotland's economy, our business community and our nation as a whole will be better off as an independent country."