As the motor vehicle population in China continues to increase at an annual rate of approximately 15%, air pollution related to vehicular emissions has become the focus of attention, especially in large cities. There is an urgent need to identify the severity of this pollution in China. Based on an investigation into vehicle service characteristics, this study used a series of driving cycle tests of in-use Chinese motor vehicles for their emission factors in laboratories, which indicated that CO and HC emission factors are 5-10 times higher, and NOx 2-5 times higher, than levels in developed countries. The MOBILE5 model was adapted to the Chinese situation and used to calculate the emission of pollutants from motor vehicles. Results show that vehicle emission is concentrated in major cities, such as Beijing, Guangzhou, Shanghai, and Tianjin. Motor vehicle emissions contribute a significant proportion of pollutants in those cities, with contribution rates of CO and NOx greater than 80% and 40%, respectively, in Beijing and Guangzhou. Urban air quality is far worse than the national ambient air quality standard. In conclusion, although China has a relatively small number of motor vehicles, most of them are concentrated within metropolitan areas, and their emissions are closely related to urban air pollution problems in large cities.