This paper presents an analysis of the effects of the COVID-19 pandemic on the air quality of the Metropolitan Region of São Paulo (MRSP). The effects of social distancing are still recent in the society; however, it was possible to observe patterns of environmental changes in places that had adhered transportation measures to combat the spread of the coronavirus. Thus, from the analysis of the traffic volumes made on some of the main access highways to the MRSP, as well as the monitoring of the levels of fine particulate matter (PM2.5), carbon monoxide (CO) and nitrogen dioxide (NO2), directly linked to atmospheric emissions from motor vehicles–which make up about 95% of air polluting agents in the region in different locations–we showed relationships between the improvement in air quality and the decrease in vehicles that access the MRSP. To improve the data analysis, therefore, the isolation index parameter was evaluated to provide daily information on the percentage of citizens in each municipality of the state that was effectively practicing social distancing. The intersection of these groups of data determined that the COVID-19 pandemic reduced the volume of vehicles on the highways by up to 50% of what it was in 2019, with the subsequent recovery of the traffic volume, even surpassing the values from the baseline year. Thus, the isolation index showed a decline of up to 20% between its implementation in March 2020 and December 2020. These data and the way they varied during 2020 allowed to observe an improvement of up to 50% in analyzed periods of the pollutants PM2.5, CO and NO2 in the MRSP. The main contribution of this study, alongside the synergistic use of data from different sources, was to perform traffic flow analysis separately for light and heavy duty vehicles (LDVs and HDVs). The relationships between traffic volume patterns and COVID-19 pollution were analyzed based on time series.