An easy method of preparing well-crystallized Sb2Se3 films and nanorods through magnetron sputtering was proposed, and their growth mechanism was examined. The microstructure, morphology, composition, and optical and electrical properties of the Sb2Se3 films depended strongly on the substrate temperature (T-Sub). Sb2Se3 films prepared at > 250 degrees C contained the orthorhombic phase without Sb2O3 phase owing to the high-purity vacuum environment. Well-crystallized Sb2Se3 films deposited at T-sub, = 325 degrees C showed compact grains with a bandgap of 1.23 eV and a high absorption coefficient of 10(5) cm(-1) in the visible region. Photoelectrochemical measurements showed that Sb2Se3 films were p-type semiconductors with excellent photoresponse. A clear photovoltaic effect with a power conversion efficiency (PCE) of 3.35% was measured for the first time by using the sputtering Sb2Se3 films as absorbers in a photovoltaic solar cell. At Tsub = 375 degrees C, highly uniform films with monodispersed Sb2Se3 nanorods were obtained. The preferential orientation of the Sb2Se3 crystals by self-organization was promoted by increasing T-sub. By using the Sb2Se3 nanorods as absorbers in a solar cell, good photoresponse and a PCE of 2.15% were achieved.