The recycling of plastic waste has attracted increasing attention because of its negative effects on the ecological environment and human health. Photoreforming is emerging as a green and promising approach for upcycling plastic waste into highly valuable chemicals and H2 fuels. Herein, an earth-abundant Ni2P/ZnIn2S4 catalyst prepared by mechanical grinding is reported to selectively photoreform various polyester plastics into high-added-value chemicals coupled with H2 evolution under mild conditions. In particular, polylactic acid (PLA) can be upcycled to pyruvic acid (PA) with high activity (745.9 μmol g−1 h−1) and selectivity (>90%). Moreover, the H2 evolution rate can reach up to 781.3 μmol g−1 h−1 catalyzed by 7.5 wt% Ni2P/ZnIn2S4. This system exhibits excellent photocatalytic performance, benefiting from efficient photogenerated charge carrier separation and transfer between Ni2P and ZnIn2S4. This study provides a viable and promising solution for simultaneously producing high-purity H2 and added-value chemicals from polyester plastic waste, demonstrating its potential for practical recycling applications.