Vehicle emissions belong to the category of near-surface sources, occur close to human activity areas, and pose a greater threat to human health than other anthropogenic pollution sources. Furthermore, the study of the spatiotemporal characteristics of near-road traffic pollution is of great significance to urban and regional ambient air quality management, and is also an important basis for vehicle emission inventories, as well as the assessment of ambient air impact. Most previous studies have analyzed the spatiotemporal characteristics of hydrocarbons (HCs), carbon monoxide (CO), nitrogen oxides (NOx), and carbon dioxide (CO2) in urban vehicle emissions over a certain time, without considering the synergistic effect of mobile source particulate matter, NOx, and volatile organic compounds (VOCs). In this study, we analyze the composition of vehicles with different emission standards from road mobile sources in Anqing City, China. National category III and IV vehicles are the main contribution sources of various pollutants, accounting for more than 60% of emissions. Although national category I and II vehicles accounted for less than 1% of the total number of vehicles, their contribution to emissions cannot be ignored, especially for CO and HCs, the contribution of which from such vehicles can reach about 7%. This is mainly due to the low level of pollution control arising from the larger emission factor and greater age of these vehicles. Furthermore, eliminating old cars and increasing the proportion of national category VI vehicles can effectively reduce vehicle pollutant emissions. In terms of the spatiotemporal distribution characteristics, highways around urban areas are also the main sources of heavy vehicles, and the emission intensity of these pollutants is also higher on national roads and highways surrounding urban areas. In addition, the presence of m/p-xylene and toluene solvent-using species is detected, which indicates that petrol vehicle emissions, LPG and petrol volatilization, and solvent-using sources contribute significantly to ozone formation in the ozone pollution process. Comparing weekdays and non-weekdays, the PM2.5 peaks on non-weekdays are significantly higher than those on weekdays, and there is no “weekend effect”, which indicates that traffic emissions have little influence on PM2.5 emissions, and may be related to energy use and industrial pollution. Overall, this study strengthens the understanding of the relationship between emissions, traffic volumes, and vehicle types on spatial and temporal scales, and emphasizes the need for further investigation and comprehensive measures to mitigate pollution from these emissions.