Separation of photo-induced charges is crucial in controlling the performance of photocatalysts, photochemical cells, and photovoltaic devices. We developed a controlled synthesis of α-In₂S₃/In₂O₃ nanowire heterostructures by a hydrothermally assisted sulfurization process. Structural characterization reveals that two distinct nanowire heterostructures: α-In₂S₃ nanoparticles decorated In₂O₃ nanowires and α-In₂S₃/In₂O₃ core–shell nanowires were obtained by controlling the pH condition during the sulfurization process. Optical characterization results show α-In₂S₃/In₂O₃ nanowire heterostructures exhibit a significantly decreased visible light emission and enhanced visible light absorption compared with the pure In₂O₃ nanowires, revealing that an efficient photo-induced charge separation efficiency exists. The band offsets of the α-In₂S₃/In₂O₃ nanowire heterostructures were determined by X-ray photoemission spectroscopy and a type-II band alignment at the interface is confirmed. Time-resolved photoluminescence results reveal that the α-In₂S₃ nanoparticles/In₂O₃ nanowires exhibit significant photo-induced carrier lifetime improvement compare with the α-In₂S₃/In₂O₃ core–shell nanowire, due to a shorter charge carrier transport path, which ensures rapid charge separation at the interface. Because of the staggered band offset which promoted effective charge separation, the α-In₂S₃/In₂O₃ nanowire heterostructures exhibited enhanced photocatalytic activities under visible light illumination, demonstrating their promising potentials in relevant photo-conversion applications.