The growing of vehicle population aggravates air pollution and threatens human health. In this study, based on the refined whole-process vehicle emission inventory considering volatile organic compounds (VOCs) evaporation emission, the CAMx model was applied to comprehensively quantify the impacts of the vehicle sector on the annual and seasonal concentrations of PM2.5 and O-3 in China. Also, the health risks caused by long-term exposure to PM2.5 and O-3 were evaluated. The model results showed that vehicle emission was an important source of severe O-3 pollution in summer, with a contribution of more than 30% in most parts of China, but not an important source of serious PM2.5 pollution in winter, with a contribution of less than 20% in heavily polluted regions in China. Compared to tailpipe emission, vehicle VOCs evaporation emission led to increases of 25% and 47% to sectoral contribution to PM2.5 and O-3. Health risk assessment results showed that attributable deaths caused by long-term exposure to PM2.5 and O-3 were 975,029 and 46,043 in 2018, to which vehicle emission contributed approximately 12.5% and 22.2%, respectively.