Photothermal reverse water gas shift (RWGS) catalysis holds promise for efficient conversions of greenhouse gas CO 2 and renewable H 2 , powered solely by sunlight, into CO, an important feedstock for the chemical industry. However, the performance of photothermal RWGS catalysis over existing supported catalysts is limited by the balance between the catalyst loading and dispersity, as well as stability against sintering. Herein, we report a core-shell strategy for the design of photothermal catalysts, by using Ni 12 P 5 as an example, with simultaneously strong light absorption ability, high dispersity and stability. The core-shell structured Ni 12 P 5 @SiO 2 catalyst with a relatively small Ni 12 P 5 particle size of 15 nm at a high Ni 12 P 5 loading of 30 wt% exhibits improved activity, nearly 100% CO selectivity, and superior stability in photothermal RWGS catalysis, particularly under intense illuminations. Our study clearly reveals the effectiveness of the core-shell strategy in breaking the limitation of supported catalysts and boosting the performance of photothermal CO 2 catalysis.