The two year scheme will give the apprentices the opportunity to earn while they learn and gain valuable skills and professional qualifications.
Apprenticeships will be available in Manchester and Hull and there will be a mixture of opportunities in customer service and commercial, train planning and engineering.
To further support their development, the apprentices will also work towards a Duke of Edinburgh Gold Award.
Emma Peel, head of sales and resourcing at The Manchester College Apprenticeship Unit, said: "Partnerships such as this with TransPennine Express ensure we lead the way as apprenticeships become even more relevant to a new generation of learners and jobseekers.
“We are committed to quality learning and employment outcomes, and look forward to helping talented young people succeed through apprenticeships with TPE."
Successful individuals will be expected to begin their apprenticeships in September 2016.