Network Rail, Flybe and McDonald's have been given "awarding body" status by the Qualifications and Curriculum Authority (QCA).
McDonald's and other businesses will be able to give their employees qualifications equal to GCSEs, A-levels and degrees in subjects such as fast-food restaurant management or track engineering.
The employer recognition scheme is being trialed in many different businesses and sectors, the QCA statement said.
It will enable the first firms to be awarded the new status to "assess, track and recognise work-place learning which would have previously been lost".
Innovation, universities and skills secretary John Denham said: "It is right that we recognise and accredit employers that have shown a commitment to training and developing their staff."
Mr Denham said the vocational qualifications would be beneficial for the country as a whole and end divisions between company training and national qualifications.
McDonald's will pilot a 'basic shift managers' course on a credit-based system in line with qualifications and credit framework (QCF) guidelines. The course covers everything managers need to know, from basic operation to market and human relations.
"Receiving official awarding body status is an important and exciting step for McDonald's," said David Fairhurst, senior vice president and chief people officer at McDonald's.
"We want to ensure that our approach to recruitment, training, and development continues to create real opportunities for social mobility."
Flybe, the budget airline, will confer qualifications from level two (GCSE at A*-C) to level four (degree) for programmes on engineering and cabin training, while Network Rail will have qualifications as high as level eight (PhD).