In response to environmental problems, China has implemented many policies to control its emission of air pollutants and CO2. As a significant source of pollutant emissions, energy use has received special attention. Shaanxi Province is a region of China with major thermal power generation, which consumes a large amount of fossil fuel and causes severe deterioration in ambient air quality. However, it is rich in natural resources that could support the development of solar energy, wind energy, and other renewable clean energies, making it a typical example of a region suitable for energy structure transformation. On the basis of environmental statistical data, field surveys, and data from the Shaanxi Provincial Bureau of Statistics, this study developed an inventory of anthropogenic source emissions of seven pollutants in 2017 in Shaanxi Province. In accordance with the established inventory, various scenarios were considered to analyze the impact of energy structure transformation on air pollutant emissions. In comparison with the Business-as-Usual scenario, the comprehensive clean energy use scenario reduced SO2, NOx, CO, PM10, PM2.5, VOCs, NH3 and CO2 emissions by 32.50%, 33.10%, 14.56%, 26.64%, 16.72%, 2.88%, 4.36% and 36.85%, respectively. Ambitious development of clean energy, such as wind and solar, could greatly reduce the emission of air pollutants, especially CO2, SO2 and NOx, that are derived mainly from fossil fuel combustion, showing that strict control of the energy structure could reduce pollutant emissions. This work is important for quantifying the impact of energy restructuring on regional air quality and providing pollution control policies for environmental managers.