Later than Palazzo Minucci-Solaini but older than that of the Encounters and Inghirami, already in a more baroque though moderate style, the Maffeiano presents the grandiose forms of the fullest and brightest period of the Renaissance. The Volterra palace remains without a secure attribution of author. It was finished towards the end of 1527, and the grandeur of the building seems to follow the structural and architectural typology of the buildings built by Roman architects. With its portal crowned with ashlar and rectangular windows with stone cornices, Palazzo Maffei presents, on the first floor, windows with jutting tympanums and, on the second floor, architraved windows, a sloping eave concludes the roof, where in the coffers is repeated the ornamental motif of the hexapetal flower that also occurs in the atrium columns.

But the beauty and the authority of the building is not limited to the exterior only if, as Raffaello Maffei tells us, in the palace there were several fragments of columns, capitals and other ornaments of the Roman theater.

Thus the façade depicting the munificence of Mons. Maffei, also showed paintings with light and gold highlights, painted by Daniele Ricciarelli, with a frieze representing a Roman triumph. The palace was purchased by Mario Guarnacci in the 18th century who, in the four rooms below, ordered the collection of Etruscan urns, thus forming the first Museum in Volterra, visited by various scholars and personalities such as the Grand Duke of Tuscany Pietro Leopoldo, as a plaque in the courtyard recalls at the beginning of the staircase. Around 1840 the palace became the property of Giuseppe Leoncini and, subsequently, of Carlo Ruggieri Buzzaglia.
The other Maffei Family Palace stands right in front of the Church of San Michele.

The south-east corner is made up of the remains of a medieval tower house that was incorporated with the construction of the seventeenth-century palace; this tower house in the 14th century was owned by the Caffarecci family. We know, from a document of the fifteenth century, that this tower was also joined by other houses, also belonging to the Caffarecci family, which were located where the palace now stands; behind the houses there was a garden and on the ground floor there were two shops, one of which was an apothecary’s.
In these houses, guests of Ser Giovanni Caffarecci, captain of the families of the priors of Florence, many people of the Medici family lodged. Here they stopped, among others Lucrezia Tornabuoni, mother of the Magnificent, and Cosimo il Vecchio, on the occasion of their trips to the Baths in Morbo.

The palace was rebuilt during the seventeenth century when it was bought by the Maffei family of which we can see the crest Above the entrance door. The design of the entrance door has been attributed to Antonio da San Gallo, while the facade of the building was built in the early 1800s based on a design by Angelo Bellucci from Volterra. Since 1901 it has been owned by the Bianchi family.