With rapid economic growth, road transport is contributing substantial adverse effects on urban air quality, especially in densely populated cities with high growth rate of GDP per capita, such as Macau. A high spatial–temporal resolution road traffic emission inventory is essential for assessment of environmental stresses imposed by local vehicle movements. To improve the accuracy and temporal–spatial resolution for emission inventory, through a bottom-up approach, link-based road traffic emission inventory with a spatial resolution of 0.1 km ∗ 0.1 km and a temporal resolution of 1 h for Macau in 2014 was developed by using a traffic model (VISUM), a road traffic emission model (TREM), the Geographic Information System (GIS), and the most up-to-date information available. Results show that the total annual emissions of CO, CO₂, PM, NO_X, and VOC in 2014 were 14,770, 413,099, 69, 1151, and 2945 tons, respectively. The estimated fuel consumption agreed well also with the statistical fuel consumption in Macau. Meanwhile, analysis of 3 scenarios on changes of road traffic emissions due to the operation of a light railway transit (LRT) system, variation on share of diesel, electric, and gasoline within the vehicle fleet, and replacement of vehicles with ones of Euro 5 and Euro 6 emission standards was carried out. This study provides a solid framework for developing high spatial–temporal resolution emission inventories for other densely populated cities of small area.