Despite the high public interest in particulate matter (PM), a key determinant for indoor and outdoor activities, the current PM information provided by monitoring stations (e.g., data per administrative district) is insufficient. This study employed the closed-circuit television (CCTV) cameras densely installed within a city to explore the spatial expansion of PM information. It conducted a comparative analysis of PM estimation effects under diverse experimental conditions based on AI image recognition. It also fills a gap by providing an optimal analysis framework that comprehensively considers the combination of variables, including the sun’s position, day and night settings, and the PM distribution per class. In the deep learning model structure and process comparison experiment, the hybrid DL-ML model using ResNet152 and XGBoost showed the highest predictive power. The classification model was better than the ResNet regression model, and the hybrid DL-ML model with the post-processed XGBoost was better than the single ResNet152 model regarding AI prediction of PM. All four experiments that excluded the nighttime, added the solar incidence angle variable, applied the distribution of PM per class, and removed the outlier removal algorithm showed high predictive power. In particular, the final experiment that satisfied all conditions, including the exclusion of nighttime, addition of solar incidence angle variable, and application of outlier removal algorithm, derived predictive values that are expected to be commercialized.