The development of the COVID-19 pandemic and the related lockdown had a major impact on vehicle traffic in cities. Based on available data from the selected city of Rzeszow, Poland, it was decided to assess changes in vehicle traffic and the impact of these changes on roadside environmental pollution. As part of the research, data from the first half of 2020 regarding vehicle traffic on selected streets of the city and on the city’s inlet routes were analyzed. For the selected road sections, changes in hourly traffic volume in 2020, compared with 2019, were also determined. With data on traffic volume, an attempt was made to estimate the impact of changes in traffic volume on air pollution in the city. Research on air pollution from motor vehicles was focused on a selected section of a city road that was equipped with an automatic air pollution measurement station located very close to the road. Additionally, at the road intersection and in the vicinity of the measuring station, a sensor was installed in the roadway to count passing vehicles. A preliminary analysis of air pollution data revealed that factors such as wind speed and direction and outside temperature had a large impact on measurement results. To eliminate the influence of these factors and to obtain data concerning only contamination originating from motor vehicles traveling along the road, an appropriate mathematical model of the traffic flow–roadside environment system was built. This model was designed to determine the air pollution in the vicinity of the road generated by traffic flow. The constructed model was verified, and the conditions for its use were determined in order to study the impact of traffic and roadside environment on the level of air pollution from harmful exhaust substances. It was shown that at certain times of the day, especially at low temperatures, other sources of harmful emissions related to home heating play a major role in air pollution in the city.