Localized surface plasmon resonances (LSPR) in near-infrared (NIR) region have been extensively studied for copper chalcogenide nanostructures, not only for the absorption enhancement but also tunable LSPR characteristics with their free carrier concentrations or defects. In the present work, one-step cation exchange method has been used to synthesize Cu2−xS nanowires with x varied between 0 and 1, including Cu2S, Cu7S4 and CuS and so forth. The plasmonic band of Cu2−xS nanowires shifts to a shorter wavelength with the increase in x, as observed in vis-NIR spectra, which is attributed to the increase in density of copper vacancies. The Cu2−xS nanowires have been used as catalysts towards the photocatalytic generation of H2 from ammonia borane (AB). Among samples with different Cu-S compositions, Cu7S4 samples exhibited the highest activity in terms of H2 evolution rate (25.54 mmol/g h). Moreover, a marked enhancement of the H2 evolution rate (157.04 mmol/g h) could be achieved after decorating the Cu2−xS nanowires with Pd nanoparticles to form the hybrid structures. The results of the present investigation may lead to an effective strategy for the design and development of LSPR materials for photocatalytic applications.