Using full solar spectrum for energy conversion and environmental remediation is a major challenge, and solar-driven photothermal chemistry is a promising route to achieve this goal. Herein, this work reports a photothermal nano-constrained reactor based on hollow structured g-C N @ZnIn S core-shell S-scheme heterojunction, where the synergistic effect of super-photothermal effect and S-scheme heterostructure significantly improve the photocatalytic performance of g-C N . The formation mechanism of g-C N @ZnIn S is predicted in advance by theoretical calculations and advanced techniques, and the super-photothermal effect of g-C N @ZnIn S and its contribution to the near-field chemical reaction is confirmed by numerical simulations and infrared thermography. Consequently, the photocatalytic degradation rate of g-C N @ZnIn S for tetracycline hydrochloride is 99.3%, and the photocatalytic hydrogen production is up to 4075.65 µmol h g , which are 6.94 and 30.87 times those of pure g-C N , respectively. The combination of S-scheme heterojunction and thermal synergism provides a promising insight for the design of an efficient photocatalytic reaction platform.