Environmental and climate protection is one of the areas of development of modern smart cities intensively exposed in the literature. Nevertheless, it often remains only a scientific postulate or a strategic record of city authorities. With these circumstances in mind, this article addresses conceptual assumptions with actual achievements in improving air quality in 16 Polish cities aspiring to be smart. In this way, an answer is sought to the following research problem: To what extent do Polish cities aspiring to be smart and operating in a developing economy realize the climate quality improvement goals exposed today by the smart city concept and the environmental requirements of the European Union? The research was conducted in a long-term perspective covering the period from 2010 (entry into force of EU air quality standards) to 2022. In addition, with reference to contemporary urban environmental studies, special attention was paid to the impact of the COVID-19 pandemic on air quality in the surveyed cities. In the course of the study, data on PM10 concentrations were used and statistically analyzed using measures of variability and cluster analysis as an unsupervised classification method. The results allow the formulation of the following key conclusions: (1) PM10 levels were systematically reduced in all 16 cities studied, which allows a positive assessment of the municipal authorities’ efforts to improve urban air quality; (2) the leaders in the effectiveness of PM10 reduction are Warsaw and Wrocław; and (3) after the COVID-19 pandemic, most of the cities studied managed to maintain or improve urban air quality. The originality of the considerations and analysis undertaken is due to the following considerations: (1) to fill the research gap in terms of the long-term assessment of the effectiveness of air quality improvement in cities aspiring to be smart and located in developing or emerging economies; (2) to make a cognitive contribution to the environmental research stream on smart city development (gaining knowledge on the effectiveness of cities’ actions to improve air quality); and (3) to conduct an analysis of the impact of the COVID-19 pandemic on air quality in Polish cities located in various provinces.