Photocatalytic cement has been receiving attention due to its high oxidation power that reduces nitrogen oxide, thus contributing to a clean atmospheric environment. However, there has not yet been a thorough investigation on the effect of photocatalytic reactions on the durability of cementitious material, the parent material. In this study, photocatalytic cement samples were exposed to nitric oxide gas and UV along with cycles of wetting and drying to simulate environmental conditions. The surface of samples was characterized mechanically, chemically, and visually during the cycling. The results indicate that that the photocatalytic efficiency decreased with continued NO oxidation. The pits found from SEM indicated that chemical deterioration, such as acid attack or leaching, did occur. However, this was not confirmed by X-ray diffraction. The hardness was not affected, probably due to the formation of CSH as evidenced by the XRD pattern. In conclusion, it was found that photocatalysis could alter cementitious materials both chemically and mechanically, which could further affect long-term durability.