BackgroundLead citrate is a precursor that can be prepared by recycling the spent lead paste of lead-acid batteries. Lead citrate is used to synthesize lead oxide, which can be repeatedly utilized for the lead-acid battery application. MethodsWe report a new application of lead citrate precursor to synthesize PbS@Cu2S nanomaterials for photocatalytic H2 production. PbS@Cu2S was prepared by microwave-assisted hydrothermal and ion-exchange processes. The electron-transfer dynamics and H2-production activity of PbS@Cu2S photocatalysts were studied. Significant FindingsA S-scheme heterojunction is proposed based on the results of Tauc plots, ultraviolet photoelectron spectroscopy, the electron paramagnetic resonance scavenger test, and in situ near-edge X-ray absorption fine structure (NEXAFS) analysis. Results of in situ NEXAFS reveal the transfer of photoexcited electrons from PbS to Cu2S. By loading an optimized amount of Cu2S, the carrier separation and photocatalytic activity of PbS@Cu2S photocatalysts are improved. This technology can transform the lead citrate precursor to the PbS@Cu2S photocatalyst with excellent high H2 production activity (3824 μmol·g−1·h−1).