Conventional semiconductor photocatalysis based on band-edge absorption remains inefficient due to the limited harvesting of solar irradiation and the complicated surface/interface chemistry. Herein, novel photothermal-enhanced catalysis was achieved in a core-shell hierarchical Cu7S4 nano-heater@ZIF-8 heterostructures via near-infrared localized surface plasmon resonance. Our results demonstrated that both the high surface temperature of the photothermal Cu7S4 core and the close-adjacency of catalytic ZIF-8 shell contributed to the extremely enhanced catalytic activity. Under laser irradiation (1450 nm, 500 mW), the cyclocondensation reaction rate increased 4.5-5.4 fold compared to that of the process at room temperature, in which the 1.6-1.8 fold enhancement was due to the localized heating effect. The simulated sunlight experiments showed a photothermal activation efficiency (PTAE) of 0.07%, further indicating the validity of photothermal catalysis based on the plasmonic semiconductor nanomaterials. More generally, this approach provides a platform to improve reaction activity with efficient utilization of solar energy, which can be readily extended to other green-chemistry processes.