Electrification of energy systems, including an increased percentage of electric vehicles on the road, is one of the primary paths to achieve zero carbon emissions. However, a reduced share of fossil fuel in transportation and industry requires a significant shift in power generation energy sources. Power generation from renewable sources is still limited and will be for the foreseeable future. Developing countries and oil-producing nations in the middle east may shift to electric vehicles, but electricity energy sources will not be easily moved to renewables., A detailed and comprehensive emission inventory was developed in a bottom-up method for a typical populated city in Iran, middle-east. The objective was to study the effects of power generation emissions on local criteria air contaminants and greenhouse gas emissions. All primary sources of emissions, including mobile sources, industries, house heating, power generation, cement and brick production facilities, fuel stations, and transportation hubs, were considered in the study. In the mobile sources section, exhaust and non-exhaust, cold and hot exhaust, and resuspended dust particles were included in the model. The methodology of developing the emission inventory is described in this study. It was found that the emission profile of a largely populated city, which is also a religious tourist attraction in the region, is highly driven by the power generation sources, despite the large population of vehicles on the road. The emission inventory study showed a contribution of 56% NOx and 97% SOx emissions by power plants to the total emissions as high sulphur heavy oil is used partially in electricity generation. Powerplants also generated more than one-third of particulate emissions. At the current state, given the significant impact of power generation on air pollution, increasing electric vehicle share will worsen the urban living conditions for a populated city unless a substantial shift in power generation energy source toward renewables happens.