The church was elevated to a cathedral only in 1844 when the diocese was officially moved from Sovana  to  Pitigliano and was dedicated to Saints Peter and Paul. The structure is that of the typical Renaissance churches with a nave with four side chapels and was commissioned by Niccolò III even if in fact it was his son Ludovico who completed the work in 1507.

The façade has the typical Baroque aspect and is the work of reconstruction works carried out in the 1700s; of the original Renaissance façade only the entrance portal remains.

The decorations of the altars are also attributable to the eighteenth-century period.