With the rapid growing of vehicle population, NOx has gradually become a key factor restricting the prevention and control of O3 pollution in China. High-resolution vehicle emission inventories are essential for the development of scientific and efficient pollution prevention and control policies. In this study, a bottom-up approach is adopted to develop a high temporal and spatial resolution vehicle NOx emission inventory for Guangzhou in 2021 based on real-time road network hourly-scale traffic data detected by 5,198 AVI devices. The study further examines the prominent emission vehicle types, emission periods, and emission hotspots in different regions (11 administrative districts, central urban areas, and noncentral urban areas) to facilitate a detailed analysis and traceability of high-pollution events. The results of the study showed that the average daily NOx emission from vehicles was 196.15 t/day and the average daily emission intensity was 15.82 kg/(dayžkm). Diesel trucks, medium & heavy diesel trucks, and diesel trucks with China III or lower emission standards are the prominent vehicles with low occupancy and high emissions. In terms of spatial distribution, HDTs are the main contributors in the non-central urban areas, while heavy passenger vehicles and light duty trucks are the main contributors in the central urban areas, and buses also contribute a slightly higher percentage compared to the non-central urban areas. To meet the demand of freight transportation, the distribution of NOx emission hotspots shows a pattern of dispersion outward along the beltway network centred on Baiyun District. A more detailed traceability analysis of the high NOx emission contribution is used to assist in the development of pollution prevention policies.