Flanking the western arch were four sculptures by J. Massey Rhind, the sculptor who had carved the figures on the southern facade of Alexander Hall. Presidents Witherspoon and McCosh occupied the lower pair of niches, with James Madison, class of 1771, and Oliver Ellsworth, class of 1766 above. A sundial, with the inscription "Pereunt et Imputantur" [They pass away and are charged to our account], graced the south side of this tower.

From an academic perspective, Pyne Library contained a number of innovations that were the result of the intimate involvement of Ernest Richardson in the building's design. Richardson pioneered the use of a standard size stack --seven and a half feet tall -- and developed a cataloging system that allowed for the collection to expand without having to reclassify large numbers of books.

Pyne Library opened in 1897 and remained in service until the construction of Firestone Library in 1947, when the structure was converted into administrative offices. In 1965, the administrative offices moved to New South and Chancellor Green was adapted for use as a student center. Pyne Library, renamed East Pyne was modified to house faculty offices and classrooms.