The two-year contract, awarded by Neptune Projects, will see a three-storey girls’ arts college on the site of the existing St John Bosco Arts College.
The campus will include a 3G synthetic all-weather sports pitch and a multi-use games area.
Maggie Farrar, executive director at National College, said: “The new building will be less rigid in design, allowing more flexibility in the way the school teaches lessons.”
Mark Thomas, regional director for Vinci Construction UK, said: “This campus will shape learning well into the future and help strengthen Liverpool’s reputation as a world class cultural hub.”
The contract win comes just days after Vinci completed work on a £22m specialist STEM (science, technology, engineering, enterprise, English and mathematics) school in Sheffield.
The two-and-a-half year Bradfield School contract included a three storey 8,606 sq m main school building and a biomass energy centre and a sports hall with four tennis courts.