The results of analysis for the content of benzo(a)pyrene are presented for the atmospheric air samples collected in 142 cities of the Russian Federation covered by the state observation network over the period 2017–2019. Trends of seasonal changes were considered, and a comparative analysis of the status of air pollution in the cities within the Federal districts of the Russian Federation was given. To characterize the spatial distribution of the benzо(a)pyrene concentrations in the atmospheric air of the Russian cities, maps of average concentrations by seasons were constructed. Correlation dependences between the average benzо(a)pyrene concentrations and the season were analyzed. The benzо(a)pyrene concentrations exceeding the health-based exposure limit [>1 maximum permissible concentration (MPC)] were recorded in the winter season from 59 cities out of 142 (41.5%), in the spring season (20%), in the summer season (9%), and in the autumn season (27.5%). For the Siberian Federal District cities the average benzо(a)pyrene concentrations in all the seasons exceeded by an order of magnitude those for the cities in the European part of the Russian Federation. The ratio of the benzо(a)pyrene concentrations for the winter and summer seasons (winter/summer > 5) was proposed as a marker of coal combustion in urban air. The main causes and factors responsible for the formation of high benzо(a)pyrene concentrations in the atmospheric air of the Russian Federation cities were identified.