First mentioned in AD 966, the church was built atop the stylobate of a Roman temple, from which a pietra serena pillar was incorporated into the church's north wall. There is also a Roman decumanus running north–south that flanks the church. Moreover, findings of nearby Lombard sepulchres indicates that the church was once an early Christian site. The church occupies a prominent position in Piazza Mino, near the Fiesole Cathedral. Due to an image inside of the Virgin Mary it appears that the church is the site of the oldest instance of veneration of the Madonna in the Diocese of Fiesole, which would form the basis for "Primerana" in the church's name.
Santa Maria Primerana was expanded in the Middle Ages. From this period, the Gothic chancel remains. A new façade was built at the end of the 16th century in the Mannerist style. The interior was decorated with sgraffito decor by Ludovico Buti.
The portico, which is constituted by an architrave supported by columns of the Ionic order, dates to 1801.
The interior consists of a single transept room. The high altar was constructed between 1745 and 1767 by
Bernardino Ciruini. On the altar is a 13th-century tablet by Maestro di Rovezzano, which depicts the Madonna and Child.
In the transept are two marble bas-reliefs by Francesco da Sangallo. One dates to 1542 and is a Self-portrait of the artist; the other dates to 1575 and is a Portrait of Francesco del Fede. Also in the transept is a glazed terracotta from Andrea della Robbia's workshop depicting the Crucifix between the Madonna, St. John, Mary Magdalene and Angels. There is, additionally, a large, painted, wooden crucifix designed in the
Giotto school from the 14th-century, which is attributed to Bonaccorso di Cino.
The faded remains of frescoes on the walls are by Niccolò di Pietro Gerini.