Scottish chef Gordon Ramsay, worth an estimated amp;#163;50 million, is 50th on the vocational rich list. His career as a chef was launched after he completed an HND course in hotel management at Banbury Technical College, near Oxford.
Sir Jackie Stewart, who won the Formula One world championship three times, worked as an apprentice mechanic in the grease-bay of his father's garage before he entered motor racing. Now he is worth an estimated amp;#163;43 million and is 54th on the list.
Jim McColl may not be a household name, but he is the only Scot in the top 10, coming in at number eight - and is believed to be worth amp;#163;435 million. He served as an apprentice engineer at the Weir pump business in Glasgow, which he later bought.
This year, Scots make up nearly a quarter of the top 100 wealthiest entrepreneurs on the vocational rich list, which is published by City and Guilds - the leading awarding body for work-based qualifications - to boost the image of vocational learning. Twenty-one out of the 100 individuals on the list were born in Scotland, with more than half setting up businesses in their home towns, and 90 per cent of them being self-made millionaires.
Gordon Ramsay is the youngest at 40, joining only three other Scots who have made their fortune before reaching their half-century. The average age of the Scots on the list is 59 years, showing, according to the publishers, that getting rich generally takes time.
Bob Coates, managing director of City and Guilds, said: "Despite harder times for some of the region's millionaires, it's encouraging to see overall that entrepreneurs from Scotland, who started their careers with a work-related qualification, continue to flourish.
"It's important to remember that the vast majority of the millionaires who feature in the Vocational Rich List survived tough trading conditions in the recessions of the Eighties and Nineties. Their success to date shows that there's a lot to be learnt from the on-the-job training that shaped their approach to doing business and we're confident that it will continue to stand them in good stead.
"In fact, the journeys these vocational entrepreneurs have taken highlight that different routes and learning styles can offer just as good an opportunity in life and can be equally rewarding."
Topping this year's list is Laurence Graff of Graff Diamonds. The so-called "king of bling" has increased his wealth from amp;#163;1.5 billion to amp;#163;2 billion in just one year to top the 2008 list and knock Sir John Caudwell, founder of Phones4U, off the top spot for the first time in four years.
Mr Graff, a Londoner, left school at 13 to take up an apprenticeship in diamonds in Hatton Garden. He then branched out into buying and selling stones and by the mid-Sixties his workshop was a haunt for the mega-rich.
His business is the only one of its kind in the world, combining everything from buying diamonds from miners through to polishing, cutting and retailing them.
WHAT MAKES THEM RICH?
Self-belief: 23 of the UK's 25 wealthiest vocational millionaires are self-made
Patience: the average age of the 25 wealthiest vocational millionaires is 61 years; within the top 100, there are only three millionaires under 40
Perseverance: among the millionaires are Paul Davidson of pipe-repair company Fluid Leader, who declared bankruptcy in 2004 but has since built an impressive second fortune of amp;#163;40 million
Graft over glamour: while the top 100 millionaires include a number of familiar names, the only household name in the top 10 is Sir James Dyson.