Ozone pollution is taking more dominant position in China than PM2.5, traditional ozonolysis catalytic materials have limited performance in humid conditions. In this study, an iron-doped basic nickel carbonate catalyst (NiCH-Fe) was successfully fabricated via a facile hydrothermal method, which could stably decompose 2.14 μg/L ozone at 60% relative humidity for 12 h with nearly 100% removal ratio. The result of the Quartz Crystal Microbalance test showed that the water molecules adsorbed on the surface of NiCH-Fe were significantly reduced as compared with that adsorbed on pure NiCH, which were favorable for the competitive adsorption of ozone. Density functional theory results proved that Fe atoms were new sites instead of Ni atoms and had stronger adsorption capacity for ozone molecules. In addition, the XPS results demonstrated that the iron atoms serving as active sites were substantially stable in the reaction. Therefore, material doped with Fe provided excellent moisture resistance and long-term stability. This work provides an effective technical method for the development of materials with high moisture resistance ability for efficient ozone catalytic decomposition.