The selective recycling of mixed plastic wastes with similar structural units is challenging. While heterogeneous catalysis shows potential for selective recycling, challenges such as complex mass transfer at multiphase interfaces and unclear catalytic mechanisms have slowed progress. In this study, a breakthrough in recycling mixed polyester wastes is introduced using heterogeneous photothermal catalysis. By adding co-solvents, the difficulties associated with multiphase interfacial mass transfer are overcome. Grain boundary (GB)-rich CeO