<p>The chemical decomposition of plastic waste into valuable fuels presents a promising strategy to mitigate environmental pollution and contribute to energy recovery. However, many waste plastics cannot be selectively depolymerized under sunlight due to the difficulty in controlling the reaction temperature and process stability. Herein, we have designed a Ni@p-SiO₂/Au photocatalyst for driving H₂ production from waste plastics (polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET)) in a far-from-equilibrium thermochemical system without CO₂ emissions. The catalyst integrates the functions of light-energy conversion and catalytic bond scission. The photothermal effect, primarily driven by Au under irradiation, not only creates a localized high-temperature environment for the polymers to melt and drawn upward through the capillary action of the porous carbon felt support but also provides the thermal energy to initiate the bond cleavage, forming small molecules. The Ni active sites further catalyze and govern the critical cleavage of C-C/C-H bonds, ensuring a controlled and efficient depolymerization pathway toward H₂ generation. The SiO₂ shell plays a crucial role in preserving the stability of both the Au and Ni sites throughout this synergistic process. PP is efficiently converted into H₂ with a selectivity that can reach as high as approximately 89%, achieving a yield of 1380 mL per gram of plastic. The system also shows robust decomposition performance for PET, PS, and real-world plastics like PP boxes, demonstrating its industrial potential. Overall, this photodepolymerization system offers a viable solution to the global plastic waste problem.</p> Graphical Abstract <p></p>