The global payment services firm announced its three-year sponsorship of the league this July. Now it is announcing an education initiative, fronted by the former football star Patrick Vieira, due to kick off this week on 20 September.
The PASS project will see Western Union fund a day's education for every pass. It hopes to fund 1m school days over the next three seasons, focusing on 11 countries: Brazil, China, Colombia, Jamaica, Mexico, Morocco, Nigeria, Senegal, Romania, Russia and Turkey.
Hikmet Ersek, Western Union president and chief executive, said: "According to Unesco, 71m bright, hardworking students globally are not enrolled in secondary or vocational education. It's a tremendous loss of economic and human potential. Through PASS, we intend to harness the power of football to build awareness of this challenge."
Vieira added: "Football was my ticket to success, but for the vast majority of young people education is the key. This campaign will benefit students, teachers and schools, particularly in places that need it most, like Senegal where I was born."
Fans will be able to increase the fund through online contributions during the season.