It had been feared colleges would lose business to work-based training organisations under the scheme, but it is emerging that colleges have taken the lion's share of the work this year.
This would mean the losers are likely to be private training organisations.
Train to Gain is supported by a network of brokers to advise businesses on how they can improve productivity through training.
Julian Gravatt, director of funding and development at the Association of Colleges, said: "We are pleased that, in an open and competitive process, colleges have done well.
"A concern we have is that Train to Gain is seen as a free opportunity and things companies were pleased to pay for they will now expect for free.
"If brokers work against that, then that will be a positive result."
Train to Gain, a development of the Employer Training Pilots, will focus on the skills needs of employers.
David Greer, project manager for Train to Gain at the Learning and Skills Council, said: "We would expect colleges, as they are bigger organisations, would do well in this process.
"Train to Gain is all about understanding all of a company's skills needs, some of which will be subsidised and some of which clearly the employers are going to have to finance themselves.
"Almost ahead of time, it will meet the requirements of the FE white paper and Bill, which comes out in the autumn."
Graham Hoyle, chief executive of the Association of Learning Providers, which represents private work-based training organisations, said: "My suspicion is that less than two-thirds will go to independent learning providers, with colleges increasing their share."
Lee Marley Brickwork employs 570 people, providing bricklayers and scaffolders to the building trade.
The firm, based in Uxbridge, Middlesex, puts staff through bricklaying NVQ levels two and three (GCSE and A-level equivalent) at Lewisham College through Train to Gain.
Robin Duntan, its health and safety training adviser, said: "The benefit is to have a qualified workforce. In the construction industry, it's becoming more and more of a requirement of the major contractors.
"We can now take on bigger contracts because we have a qualified workforce and, because we invest in and train our workforce, they feel a lot more valued and willing to stay in our employ."
The LSC says it is anxious, through Train to Gain, to strengthen the link between colleges and employers.
Before the scheme was introduced, 18 per cent of businesses were using college for their training.
The scheme is also seen as laying down the gauntlet to employers themselves, who the Government wants to do more for the training of their staff and invest more of their own cash in skills development.
The focus has been on level 2 qualifications, which are regarded by the Department for Education and Skills as a minimum requirement for career progression as well as general life skills.
The LSC claims employers, after extensive consultation, were unanimous in their support for the kind of service Train to Gain is offering.
A government-commissioned study by the Institute for Fiscal Studies earlier this year showed only 10 to 15 per cent of the training carried out under employer training pilots was additional to what businesses would otherwise have provided at their own expense.
The LSC said the presence of brokers would mean that the money would be more clearly focused under Train to Gain, ensuring that most of the training activity is additional.