The move is part of its Workforce Plus action plan, published last week, which aims to get 66,000 Scots in seven priority areas off benefits and into work over the next four years.
Such workers represent "a huge untapped potential for Scotland's economy,"
Allan Wilson, Deputy Lifelong Learning Minister, said.
Mr Wilson unveiled the plan in Clydebank along with Malcolm Chisholm, Communities Minister, while visiting the Strive project (Support and Training Results in Valuable Employees).
Aiming to bolster attitudes, confidence and communication skills, it began in April following a visit by Jack McConnell, the First Minister, to Harlem, New York, where the programme originated.
Responsibility for skills training to make people more employable is part of the work undertaken by a range of bodies, including the executive, the enterprise agencies, the Scottish Funding Council for Further and Higher Education, Communities Scotland and the Whitehall Department of Work and Pensions.
Together they spend an estimated pound;500 million on employability every year - although that does not include pound;1 billion of expenditure on lifelong learning because of the difficulty of separating out activities in colleges and universities which specifically support employability.
Mr Wilson commented: "Making better use of this significant investment will not only help boost Scotland's economy, but will transform lives and communities for the better."
Ministers acknowledge the considerable scale of the work that is already being done: a third of activity in colleges in 2003-04 was accounted for by students who came from the most deprived areas, the funding council has launched an action plan to widen access still further, pound;65m will have been invested by 2008 to improve adult literacy and numeracy, and the enterprise organisations are committing pound;15m a year to vocational training for those with short or medium-term employment goals.
In addition, the executive has begun to take action in schools to make sure the dole queue is not leavers' first destination. This includes the strategy to prevent youngsters getting stuck in the NEET group (not in education, employment or training), the Determined to Succeed enterprise agenda, the skills for work courses and improving links between colleges and schools.
But the executive's employability framework suggests these initiatives may not be joined up. "In the light of the lessons learned while developing Workforce Plus, we will review the current range of education and skills programmes related to employment available in Scotland, to check that they are well aligned and meet the needs of individuals and employers," the report states.
The first action will be targeted on those parts of the country with the highest number of jobless. These are Glasgow, North and South Lanarkshire, Renfrewshire, Inverclyde, Dundee and West Dunbartonshire, which will receive a total of pound;11.2m during the next two years.
The aim is to reduce the numbers dependent on benefits in these areas by 30,000 by 2007 and 66,000 by 2010.
In Scotland, the executive's plan notes, there is no "employability service". It adds: "What we appear to have is a competitive free-for-all which, although individually can provide a good service, is disjointed and complicated. Funders of these services therefore may not receive the best value for their money."
The action plan involves setting up a national partnership which will include the key training and employment bodies along with local authorities, the funding council, Careers Scotland and Learndirect Scotland.
The group will be expected to monitor local employability and set performance indicators to ensure targets are delivered. Ministers want to see a better return from agencies providing training and work experience.