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(1) Background: The increase in cardiovascular risk related to air pollution has been a matter of interest in recent years. The role of particulate matter 2.5 (PM2.5) has been postulated as a possible factor for premature death, including cardiovascular death. The role of long-term exposure to PM10 is less known. The aim of the study was to assess the individual relationship between air pollution in habitation and the development of coronary artery disease. (2) Methods: Out of 227 patients who underwent coronary angiography, 63 (38 men and 25 women) with a mean age of 69 (63–74) years, with nonsignificant atherosclerotic changes at the initial examination, were included in the study. The baseline and repeated coronary angiography were compared to reveal patients with atherosclerotic progression and its relation to demographic and clinical factors and exposure to air pollution in the habitation place. (3) Results: In the performed analysis, we found a significant correlation between Syntax score in de novo lesions and BMI (Spearman's rho −0.334, p = 0.008). The significant and strong correlation between median annual PM10 values of 20 µg/m3 and at least 25 µg/m3 in air pollution and the risk of de novo coronary disease was noticed (Spearman's rho = 0.319, p = 0.011 and Spearman's rho = 0.809, p < 0.001, respectively). (4) Conclusions: There is a positive correlation between long-term exposure to PM10 air pollution and coronary artery disease progression, demonstrated by the increase in Syntax score. The presented analysis revealed increased morbidity at lower PM10 concentrations than generally recommended thresholds. Therefore, further investigations concerning air pollution's influence on cardiovascular risk should be accompanied by promoting lifestyle changes in the population and revisiting the needs for environmental guidelines. [ABSTRACT FROM AUTHOR]