Rapid industrialization and urbanization have caused severe air pollution in the Guanzhong basin, northwestern China, with heavy haze events occurring frequently in recent winters. Using the NCEP reanalysis data, the large-scale synoptic situations influencing the Guanzhong basin during wintertime of 2013 are categorized into six types to evaluate the contribution of synoptic situations to the air pollution, including “north-low”, “southwesttrough”, “southeast-high”, “transition”, “southeast-trough”, and “inland-high”. The FLEXPART model has been utilized to demonstrate the corresponding pollutant transport patterns for the typical synoptic situations in the basin. Except for “southwest-trough” and “southeast-high” (defined as favorable synoptic situations), the other four synoptic conditions (defined as unfavorable synoptic situations) generally facilitate the accumulation of air pollutants, causing heavy air pollution in the basin. In association with the measurement of PM2:5 (particulate matter with aerodynamic diameter less than 2.5 µm) in the basin, the unfavorable synoptic situations correspond to high PM2:5 mass concentrations or poor air quality and vice versa. The same analysis has also been applied to winters of 2008–2012, which shows that the basin was mainly influenced by the unfavorable synoptic situations during wintertime leading to poor air quality. The WRFCHEM model has further been applied to simulate the selected 6 days representing the typical synoptic situations during the wintertime of 2013, and the results generally show a good agreement between the modeled distributions and variations of PM2:5 and the corresponding synoptic situations, demonstrating reasonable classification for the synoptic situations in the basin. Detailed meteorological conditions, such as temperature inversion, low-level horizontal wind speed, and planetary boundary layer, all contribute to heavy air pollution events in the basin under unfavorable synoptic conditions. Considering the proportion of occurrence of unfavorable synoptic situations during wintertime, reduction of emissions is the optimum approach to mitigate the air pollution in the Guanzhong basin.