The university began building a library before the first brick was laid for the campus. The first book, a copy of sermons distributed by the U.S. Congress to each of the states, was given to the newly established university in 1792 and placed in a school in New Bern until suitable facilities could be built in Chapel Hill.

Through most of the first century of the university, there were three libraries on campus: the University Library, much of which had been purchased by UNC president Joseph Caldwell on a trip to Europe in the 1820s, and the separate libraries of the Dialectic and Philanthropic Societies. While the University Library languished, the society libraries were where many students turned to find books to support their studies and for general reading. The three libraries were merged in 1885, and the University Library was formally established as a separate unit of the university in 1905.

The first building built to house the University Library was Smith Hall (now historic Playmakers Theatre), which opened in 1851. In an arrangement that was indicative of the size and importance of the library at the time, the building was also used as a ballroom, with movable shelves that could be pushed against the wall to make room for dancers. UNC's first dedicated research library opened in 1907 with support from Andrew Carnegie. The Carnegie Library (later renamed Hill Hall) represented the university's commitment to building a research library to support its growing needs.

The rapid expansion of the university through the twentieth century is mirrored by the continued construction and expansion of library buildings. The landmark Wilson Library (originally known as the University Library) opened in 1929, with additions added to hold more books and archival collections in 1952 and 1977. The university opened a dedicated House Undergraduate Library in 1968 and a new, modern library building, Davis Library, in 1984. After Davis Library opened, Wilson Library was renovated to be house special collections on campus.

The libraries have grown and changed to adapt to the digital age, often leading the way on campus. They began using a computer catalog in 1969 and opened one of the first public computer labs on campus in the 1980s. Documenting the American South, a digital library program started in the mid-1990s, received national recognition for making rare and hard-to-find primary sources about southern history easily accessible online. By the 2010s UNC Libraries was consistently ranked, in number of volumes, as one of the top twenty academic libraries in the country.