The territory of Vescovado di Murlo has been inhabited since ancient times, as evidenced by some findings of residential buildings and industrial use buildings (located in Colombaio) with attendance between the fifth and second century BC, contemporary to the development phase of the nearby site of Poggio Civitate.
The hamlet is the result of the union in modern times of two adjacent medieval villages: the northern one, called Andica or Antica due to the presence of an old castle, as hypothesized by the historian Emanuele Repetti, which was owned by the Ardengheschi counts before the establishment of the vescovado di Murlo; and the southern one, the village of Tinoni, known for the presence of a hospital dedicated to San Leonardo documented between the seventeenth and eighteenth centuries. The toponym Vescovado comes from the historic territorial district which from 1189 to 1778 constituted the territory of Murlo as the direct property of the bishop of Siena.
Following the expansion of the village in the twentieth century, Vescovado has become the main town of the municipality Murlo, as well as the municipal center, although the population is slightly exceeded by the nearby village of Casciano.
At the center of the town is the church of San Fortunato, a modern parish church that has inherited its title from the ancient church of Murlo. Built in a style reminiscent of brutalism, it was consecrated in 1972, in a place where previously stood a chapel, heavily damaged by a flood in the sixties. Inside the church there is an interesting polyptych depicting the Madonna with Child and Saints by Benvenuto di Giovanni (1475) and an 18th century processional machine in gilded and painted wood.
In Vescovado there are also the chapel of the Nativity of Mary and the oratory of San Leonardo, called the "Madonnino" of Tinoni.