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The "unique" book - a commentary on the bible - was printed in Venice in 1481 and then bound in England the following year.
Adding to its significance, the book contains recycled fragments of indulgences printed by England's first printer William Caxton, which were used as sewing guards. Indulgences were granted by the Catholic Church and gave full or partial remission of temporal punishment for sins.
University of Otago special collections librarian Donald Kerr said the book, which was part of Canon William Shoults' collection and donated to Selwyn College by his widow at the end of the 19th century, was one of many examples of book binding which would be on display as part of the exhibition From Pigskin to Paper: The Art and Craft of Bookbinding.
Dr Kerr said the book was his favourite in the university's collection and not just because of the age of the binding.
"The fact that the bible text is in the middle and all the rest around it is commentary is amazing. It is an impressive design.
"If you tried to create that today, you would have a hard job," he said.
He was also intrigued how the book ended up in Oxford, where it was bound by Rood and Hunt, after being printed in Venice and how the binder got hold of the fragments printed by William Caxton about two years earlier.
Dr Kerr said both the age of the binding and the origins of the fragments were identified by Christopher de Hamel, who examined the book when he was researching a book on medieval manuscript in about 1980.
Other notable items on display at the exhibition would include a Louis XIV binding, examples of recycling using medieval manuscripts and samples of styles by Edgar Mansfield, the Anglo-New Zealand binder.
The exhibition runs from December 20 to March 22 next year in the de Beer Gallery at the Otago University library.