Exeter College has become the first site in the country to achieve top grades in both elements of Ofsted's new enhanced inspections.
The education watchdog marked the college Outstanding in seven out of eight categories.
The college was also rated Strong for "meeting the skills needs of the area".
Principal John Laramy said it was an "exceptional sector-leading outcome" and thanked the "amazing learners, apprentices, staff and governors".
The Local Democracy Reporting Service said a team of 21 inspectors visited the college at the end of 2022 to review areas including quality of education, personal development and adult learning.
It had been eight years since the previous inspection.