Professor Geoff Layer, vice-chancellor of University of Wolverhampton, was appointed to the voluntary role by chiefs in the Cabinet Office Disability Unit.
The ambassador roles have been created in the department to help ensure businesses do "all they can" to support their disabled customers and employees.
The move was made by Justin Tomlinson, Minister for Disabled People, Health and Work, at the same time as the National Disability Strategy was launched.
Professor Layer said: "I am delighted to have been appointed as the disability and access ambassador for the universities sector.
"Without a doubt, there are improvements in the sector that need to be made, especially in light of the pandemic where support for disabled students and staff became more important than ever.
"We need to make sure that our disabled students have time, information and guidance in order to make the right decision for them, as well as access to the support they need and to have it all in place before they start their studies. We must also ensure that disabled staff are supported to carry out their roles through an inclusive and equitable approach.
"I am extremely proud to have been selected to help drive positive change to enhance the disabled student journey into higher education and to ensure that the needs of disabled staff are at the forefront of any organisational development."
The ambassador roles are voluntary posts, undertaken for a maximum of three years and supported by the Cabinet Office Disability Unit. They have been appointed as industry leaders who help to drive improvements in the accessibility and quality of services and facilities in their sector for disabled people, as consumers and employees.
Justin Tomlinson MP said: "I am very excited to welcome this incredible, impressive group of people as new disability and access ambassadors. They will help support the existing team with our programme to increase access for disabled people across a wide range of private sector industries, and I am really looking forward to working with them."
The current ambassadors have been helping industry and the Government in their response to the Covid-19 crisis and supporting work to develop the National Disability Strategy.
The 12 posts include four new sectors which have been added to the existing programme. These additional posts will work with the energy industry, hospitality (pubs and restaurants), private housing and universities.
The new appointments also cover airports, arts and culture, banking, buses, creative industries, insurance, rail travel, and the retail sector, whose posts all became vacant at the end of previous ambassadors’ tenure.
They will join colleagues already representing advertising (brand and design), the built environment, countryside and heritage, technology and web design.