Presently, most of the population has been facing a string of severe climate change problems that primarily come from the intensive emission of nitric oxide (NO), which requires a practical approach to sustain our living conditions. Herein, Ag nanoparticles-decorated ZnSn(OH)6 microcubes (Ag:cZHS) photocatalysts were synthesized rapidly and used for photocatalytic NO removal under solar light activation. The properties of the newly prepared photocatalysts are comprehensively characterized by a series of routine methods. The NO removal performance over the ZnSn(OH)6 microcubes (c:ZHS) photocatalysts was increased markedly upon being combined with Ag nanoparticles through the surface plasmon resonance effect. The contribution of e−, h+, •OH, and •O2 was extensively investigated through trapping tests and electron spin resonance analysis (ESR). Also, the by-products and apparent quantum efficiency of the cZHS photocatalysts were studied.