He was born in Florence, on his mothers side the grandson of a painter. Although he was precocious and apprenticed at a young age to Jacopo Vignali, Dolci was not prolific. "He would take weeks over a single foot", according to his biographer Baldinucci. His painstaking technique made him unsuited for large-scale fresco painting. He painted chiefly sacred subjects, and his works are generally small in scale, although he made a few life-size pictures. He often repeated the same composition in several versions, and his daughter, Agnese Dolci, also made excellent copies of his works.
Dolci was known for his piety. It is said that every year during Passion Week he painted a half-figure of the Savior wearing the Crown of Thorns. In 1682, when he saw Giordano, nicknamed "fa presto" (quick worker), paint more in five hours than he could have completed in months, he fell into a depression.