The atmospheric composition in urban areas is one of the primary tasks in air pollution studies. The research aims to provide a statistically reliable assessment of the atmospheric composition climate of the city of Sofia—typical and extreme features of the special/temporal behavior, annual means, seasonal and diurnal variations. For that purpose, extensive numerical simulations of the atmospheric composition fields in Sofia city have been performed. Three models were chosen as modeling tools. We used WRF as a meteorological pre-processor, CMAQ as a chemical transport model, and SMOKE as the emission pre-processor of Models-3 system. We developed the following conclusions. The daily concentration changes of the two essential air pollution species—nitrogen dioxide (NO2) and fine particle matters (FPRM, particulate matter (PM2.5), which has a diameter between 0 and 2.5 micrometers)—have different magnitudes. Second, the emissions relative contributions to the concentration of different species could be different, varying from 0% to above 100%. The contributions of different emission categories to other species surface concentrations have various diurnal courses. Last, the total concentration change (ΔC) is different for each pollutant. The sign of the contributions of some processes is evident. Still, some may have different signs depending on the type of emissions, weather conditions, or topography.