Born in Lippiano (Città di Castello) into a humble family, Pieralli showed a talent for poetry from a young age. She was self-taught and caught the attention of many wealthy perugino families who hired her as a tutor for their children. She was a member of the Accademia di letteratura e musica di Perugia alongside artists such as Francsco Bartoli, Ariodante Fabretti, Giovanni Pennacchi and Cesare Massari. She also had links with the Accademia dell’Arcadia, Accademia Spolentina, Accademia di San Sepolcro as well as the Infecondi di Prato, Euteleti di San Miniato and Liberi di Città di Castello. A proponent of the Italian Risorgimento, she became renowned for her patriotic poetry. By government order, she became a history and geography teacher at the Istituto Normale Superiore Femminile di Perugia in 1861, also becoming the headmistress of this school until her death in Perugia in 1865. In 1891, the Liceo Statale Assunta Pieralli was named after her.
