Sb₂S₃ is a promising photoactive material that has attracted extensive research attention, owing to its excellent optical and electrical properties. Sb₂S₃ has a one-dimensional ribbon structure, and the growth direction of the ribbons significantly changes the carrier transport characteristics of the Sb₂S₃ thin-film, thereby influencing the performance of Sb₂S₃ photoelectric devices. In this study, Sb₂S₃ thin-films are successfully prepared using hydrothermal synthesis. By adjusting the hydrothermal temperature, Sb₂S₃ thin-films realized the preferred change of orientations: from (hk0) to (hk1). When the hydrothermal temperature is 140 °C, the Sb₂S₃ thin-film exhibits (2 2 1) and (2 1 1) preferential growth. The device parameters of Sb₂S₃ solar cells based on (hk1)-oriented Sb₂S₃ thin-film are effectively improved compared with those based on (hk0)-oriented Sb₂S₃ thin-film, and their power conversion efficiency reaches 5.56%. This study may provide guidance for the hydrothermal synthesis of Sb₂S₃ optoelectronic materials and devices with desirable preferred orientations.