He was born Francesco Todeschini Piccolomini in Siena. As the nephew of Pius II by his sister Laodamia, he was received into favour by that pontiff, who permitted him to assume the name and arms of the Piccolomini family, and raised him, when only twenty-two years of age, to the see of Siena and the cardinalate. He was employed by subsequent popes in several important legations, as by Paul II at the diet of Ratisbon, and by Sixtus IV to secure the restoration of ecclesiastical authority in Umbria.
Amid the disturbances consequent upon the death of Alexander VI he was, by the not wholly disinterested influence of Cardinal Rovere, elected pope on September 22, 1503, his installation taking place on the October 8 following. He at once took in hand the reform of the papal court and arrested Caesar Borgia; but after a brief pontificate of twenty-six days he died (October 18, 1503) of an ulcer in the leg, or, as some have alleged, of poison administered at the instigation of Pandolfo Petrucci, governor of Siena.
After the death of Alexander VI, the conclave could not unite on the principal candidates, d'Amboise, Rovere, and Sforza; hence the great majority cast their votes for Piccolomini, who though only sixty-four was, like his uncle, tortured with gout and was prematurely old.
He took the name of Pius III in honour of his uncle, was crowned on 8 Oct., after receiving priestly and episcopal orders.
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