Roadside vegetation helps to retain air pollutants emitted by road traffic. On the other hand, its presence makes it difficult to ventilate street canyons. The paper examines the influence of vegetation on the dispersion of air pollution generated by road traffic, using the example of two street canyons—both-sided and one-sided street canyons. The study was conducted taking into account the actual emission conditions occurring on the analyzed road sections estimated using the HBEFA methodology. Subsequently, a three-dimensional pollution dispersion model named MISKAM was employed to simulate the air pollutant dispersion conditions in the analyzed street canyons. The modelling results were compared with the measurement data from air quality monitoring stations located in these canyons. The obtained results indicated that the presence of vegetation can significantly impact on the air dispersion of traffic-related exhaust and non-exhaust emissions. The impact of vegetation is more pronounced in the case of a street canyon with dense, high-rise development on both sides than in the case of a street canyon with such development on only one side. The results for the both-sided street canyon demonstrate that the discrepancy between the scenario devoid of vegetation and the scenario with vegetation was approximately 5 µg/m3 (10%) for PM10 and approximately 54 µg/m3 (45%) for NOx, with the former scenario showing lower values than the latter. Nevertheless, the scenario with the vegetation exhibited a lesser discrepancy with the air quality measurements. Vegetation functions as a natural barrier, reducing wind speed in the street canyon, which in turn limits the spread of pollutants in the air, leading to pollutant accumulation near the building walls that form the canyon. Consequently, atmospheric dispersion modelling must consider the presence of vegetation to accurately evaluate the effects of road traffic emissions on air quality in urban areas, particularly in street canyons. The results of this study may hold importance for urban planning and decision-making regarding environmental management in cities aimed at improving air quality and public health.