Road transport is one among the sources of air pollution in a city, which results in lowering the comfort of life and increases the occurrence of respiratory diseases. The level of pollutants emitted in the city is variable, and it depends on the type and nature of the source and the manner of land development. For this reason, the purpose of the article is an attempt at a spatial (inner) diversification of a city in terms of air quality, using a study of perception and semantic differentials (SD). The research, which covered the period from June to November 2021, was performed in Kielce—the Polish Smart City—among local experts, people well acquainted with the city and knowledgeable about air quality and the impact of pollution on human health. The results allowed the demarcation of areas with the best and the worst parameters in terms of air quality within the city. Verification of the survey was carried out using the ADMS-Roads (Atmospheric Dispersion Modeling System) software for modeling pollution levels and GIS software, using data on road traffic. The verification allowed checking whether the respondents participating in the research accurately evaluated the city space. The modeling proved that within the two selected areas, the pollution level is similar, and it does not exceed the permitted values. This might indicate that in society there is still low awareness of air quality, particularly in terms of knowing the sources of pollutants and their impact on human health, and perception of areas with the best and the worst air quality was the result of an analysis of the manner of land development and its morphology.