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Recent studies have shown that tropospheric ozone, fine particulate matter and nitrogen dioxide are the urban air pollutants of major concern regarding human health effects. Monitoring air quality is a challenge in several cities, such as Rio de Janeiro, where the number of fixed-site air quality monitoring stations and their spatial distribution are insufficient to assess the extent of atmospheric pollutants. However, despite this lack of resources, the data obtained by mobile stations are a valuable means of determining which areas are experiencing critical air quality conditions, and provide key information for an air quality management program. The main purpose of this study was to conduct a critical analysis of data obtained by the Municipal Department of Environment and Climate (SMAC) mobile station in the period 2010–2018. Concentrations determined for particulate matter with a diameter ≤2.5 µm (PM2.5), O3, NO2, SO2 and CO showed that PM2.5 and O3 are the pollutants of major concern, and that the north of the city has higher air quality indices for these compounds. In addition, the south-west district had relatively high ozone levels, probably owing to low concentrations of NO2 in a volatile organic compound (VOC)-limited ozone formation regime. These factors should be considered by the municipal government in future discussions of control strategies for managing the city’s air quality. This study also shows the value of mobile stations in making a preliminary survey of pollutant concentrations, mainly in countries with limited financial investment in air quality management.