The Piccolomini Library was built around 1492 by Francesco Todeschini Piccolomini (became Pope Pius III) to honour the memory of his uncle, Enea Silivio Piccolomini (Pope Pius II). The library was built on the north-west side of the cathedral and originally housed rich bibliographical books collected from Rome.

The room contains 10 large frescoes made between 1505 and 1507 by Bernardino di Betto (also known as Pinturicchio) which depict the life of Pope Pius II (Enea Silivio Piccolomini). The floor contains the Piccolomini family symbol in ornamental blue majolica tiles in rhomboid shapes with a gold half moon.
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