For many years, Volta delayed marriage due to his dedication to his scientific research and perhaps also due to his initial religious inclinations. He considered the life of a scientist as potentially incompatible with the responsibilities of marriage.

At the age of 49, Alessandro Volta married Maria Teresa Peregrini, the daughter of Count Ludovico Peregrini. This union marked a significant turning point in his personal life.

Alessandro and Maria Teresa Volta had three sons: Giovanni, Flaminio, and Luigi. Volta seemed to be devoted to his family after they were born.

After his retirement, Volta spent his time in Como, enjoying family life and pursuing his interests at a more relaxed pace. He maintained a close relationship with his sons and remained active in his community.