Sixteen years of hourly atmospheric pollutant data (1996â2011) in the Metropolitan Area of São Paulo (MASP), and seven years (2005â2011) of data measured in the Metropolitan Area of Rio de Janeiro (MARJ), were analyzed in order to study the extreme pollution events and their return period. In addition, the objective was to compare the air quality between the two largest Brazilian urban areas and provide information for decision makers, government agencies and civil society. Generalized Extreme Value (GEV) and Generalized Pareto Distribution (GPD) were applied to investigate the behavior of pollutants in these two regions. Although GEV and GPD are different approaches, they presented similar results. The probability of higher concentrations for CO, NO, NO2, PM10 and PM2.5 was more frequent during the winter, and O3 episodes occur most frequently during summer in the MASP. On the other hand, there is no seasonally defined behavior in MARJ for pollutants, with O3 presenting the shortest return period for high concentrations. In general, Ibirapuera and Campos Elísios stations present the highest probabilities of extreme events with high concentrations in MASP and MARJ, respectively. When the regions are compared, MASP presented higher probabilities of extreme events for all analyzed pollutants, except for NO; while O3 and PM2.5 are those with most frequent probabilities of presenting extreme episodes, in comparison other pollutants. Keywords: Air pollutants, Extreme events, Megacities, Ozone, Particulate matte