He was the youngest son of Giuseppe Guami and Ortensia Bedini and a pupil of his father. The first records of his activity date from January 16, 1615, the day he replaced his brother Vincenzo as organist at the cathedral in his home town. . On September 15, 1635, he was then elected superintendent of the Chapel of the Signoria in Lucca, a post he held until his death. In addition to liturgical works, Valerio Guami also wrote scenic works for the ceremonial of the bags (elections of the magistrates of the Republic of Lucca) in 1636 as well as motets. Luigi Nerici (1879) also mentions several oratorios, including "Christo alla colonna" (1636) for the monastery of Santa Maria Nera, which must be considered lost.
However, its importance is attributed above all to two now lost works from 1636, which would have marked the beginning of two important musical genres in Lucca: The oratorio "Cristo alla colonna" for the church of S. Maria Corteorlandini.