Piisimi is first mentioned in 1573, and confirmed as a member of the Gelosi troupe in 1574. she would in fact have been active earlier, as it was known that her lover, actor Adriano Valerini from Verona, left her for Vincenza Armani, who died in 1569, four years before 1573.
Piisimi combined her acting with singing, dancing and by writing music and was reportedly admired also in these fields.
On 24 July 1574, she performed for Henry III of France in the role of Pallas Athena in Venice, where she received great praise.
In 1589, the Gelosi troupe performed in Florence at the wedding of Grand Duke Ferdinando I de' Medici and Christina of Lorraine.
At this event, the "rival prime donne" Vittoria Piisimi performed as the gypsy in Zingara and Isabella Andreini as the madwoman in La Pazzia d'Isabella.