The state of air pollution monitoring in Kyiv city was investigated. There were discussed the relevance of observation system optimization, advantages and disadvantages of the current monitoring network for air pollution in the urban atmosphere. The united complex approach was used for justification of mentioned optimization, which was combined with emission inventories databases, meteorological air pollution potential characteristics, ratified ground-based measurements data of main pollutants, and demographic urban features. The paper discusses main meteorological parameters which drive pollutants’ dispersion. Analysis provide evidence of its huge impact for the pollution regime formation and tendency to the decline of air quality, which must be taken in consideration during optimization for atmospheric air monitoring. The process of optimization for atmospheric air monitoring takes into account the orographic urban features used mainly for the purpose of statistically valid data provision. Therefore, in small microclimatic zones the monitoring sites are located within relief bodies, which are representative for the area. The research estimates results of boundary pollutants’ content caused by middle and high stationary emission sources, defined from the methodology connected with combined IEM diffusive model. Analysis of observations confirms the accuracy of defined structure for urban pollution fields. The combine usage of modeling results and observations allows increasing of atmospheric air quality estimations and helps to optimize the network with minimal amount of necessary representative sites.