Nano-TiO2 combined with cement slurry can be utilized to degrade nitrogen oxides (NOx) in vehicle exhaust, making it an excellent photocatalytic material for air purification. In practice, environmental factors can significantly affect the photocatalytic performance. In this study, a vehicle exhaust test system was developed, and the test methods and evaluation criteria for the degradation test are provided. This study investigated the photocatalytic degradation of NO2 using nano-TiO2 cement slurry through laboratory tests. The effects of temperature, relative humidity, ultraviolet (UV) radiation flux, cement slurry thickness, surface dust adherence, and the number of water rinsing cycles were examined. Additionally, nano-TiO2 cement slurries were applied to an expressway toll station. The results showed that the efficiency of photocatalytic degradation was significantly influenced by temperature and UV radiation flux, while the thickness of the cement slurry had minimal impact. The photocatalytic degradation efficiency was negatively correlated to the relative humidity, when the relative humidity of the cement slurry specimens was high. This is because the excess water (H2O) competes with NO2 for adsorption. The photocatalytic performance of the samples was significantly reduced by surface dust and rain erosion, as both led to a decrease in the amount of nano-TiO2 participating in the reaction. Furthermore, the photocatalytic material has wide-ranging potential applications. The findings of this study would support the promotion of environmentally friendly roads as a strategy to combat air pollution.