The apprenticeships will provide on-the-job training for prisoners, providing them with a direct route into work upon release.
This has been made possible by the government changing the law regarding apprenticeships.
Previously, apprenticeships were conducted under a designated apprenticeship agreement, which was legally classed as an employment contract.
The new law makes it possible for prisoners to undertake apprenticeships without the need for such an agreement.
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The new initiative is estimated to recruit up to 300 prisoners, eligible for day release and nearing the end of their sentence, by 2025.
Jill Cotton, career trends expert at Glassdoor, said the apprenticeship scheme represented a creative way for employers to plug skills gaps in their workforce.
She told HR magazine: "Continued tight labour market conditions mean that hiring will still be challenging for many businesses through this year and into 2023. Creative thinking from employers can unlock new talent pools by seeking out overlooked workers, including those who have spent time in prison.
"A criminal record should not be a barrier to employment, and the new apprenticeship scheme is a positive step forward in upskilling those who have had time out of the workforce."
Employers should judge offenders on a case-by-case basis, Cotton added.
She said: "Employers need to assess whether a candidate's criminal record impacts or is relevant to the role they are hiring for. And, like any other application, whether the job seeker's qualifications, skills and experience match the job specification.
"Consider also the circumstances of the conviction, for example, the age and nature of the offence that took place and its seriousness. And be transparent in your hiring process, as this will establish trust between the company and the applicant."
Sheffield City Council, Co-op and Premier Foods are among the businesses who will take part in the scheme over the coming months.
Helen Redfern, chief people officer at Kier, said: "This pioneering scheme allows us to diversify our workforce further, whilst benefitting prisoners who are nearing the end of their sentence, as well as reducing the likelihood of reoffending, benefitting communities across the country.
"Being one of the first employers to take part in the scheme builds on the work we have already done through Making Ground, our prison engagement and employment programme, which is designed to support serving prisoners and prison leavers into sustainable employment in the construction industry."
