In this work, an efficient method for the copper-catalyzed ring-opening hydrolysis of silacyclobutanes to silanols was developed. This strategy has the advantages of friendly reaction conditions, simple operation, and good functional group compatibility. No additional additives are required in the reaction, and the S-S bond can also be introduced into the organosilanol compounds in one step. Furthermore, the success at the gram scale demonstrates the great potential of the developed protocol for practical industrial applications.