Porous flowerlike Cu₂S microspheres were synthesized through a solvothermal method employing CuCl and thiourea as Cu and S sources, respectively, and PVP as a surfactant. The as-prepared products have regular spherical shapes and uniform sizes around 1.8 µm, which are composed of 30–50 nm thick nanosheets with a lot of pores less than 5 nm. Time-dependent experiments showed that there were three main stages in the formation procedure. During morphology evolution, initial irregular aggregations could be transformed to long rods and then transformed further to final microspheres. A possible growth mechanism based on Ostwald ripening was proposed. The photovoltaic property test has also been conducted and these Cu₂S microspheres have a higher photocurrent density than that of Cu₂S nanoparticles.