Industrial emissions are a central environmental concern, particularly with respect to the spatial distribution of major enterprises and the identification of key determinants. Traditional research has largely focused on characterizing the current status of these enterprises, but this approach exhibits several notable shortcomings. These include a lack of regional statistical analysis, an absence of a comprehensive industrial typology, inadequate cross-evaluation of enterprise scale and pollution emissions, and insufficient exploration of socioeconomic correlations. We introduce a multifaceted evaluation framework for Key Environmental Supervision Units (KESUs), focusing on key industrial classifications and their underlying development drivers. The analysis utilized a comprehensive dataset covering 153,107 individual KESUs across six categories from 2020 to 2024, incorporating distribution patterns across 31 provincial-level regions, 28 industrial classifications of national economic activities, and 18 socioeconomic impact factors. The results showed that KESUs in East China accounted for 41.7% of the total, with the highest concentrations in industrialized cities and economically developed zones. Manufacturing was identified as the dominant industrial classification, with chemical raw materials and products comprising the largest subcategory (13.0% of total KESUs in 2024). Atmosphere KESUs and water KESUs represented the largest proportions, accounting for 29.7% and 25.3% of single-type KESUs, respectively. This study provides a systematic analysis of KESUs, offering a detailed mapping of distribution patterns, emission characteristics, and control challenges for major pollution sources. The findings can provide critical insights to support decision-making aimed at improving regional pollution source management and advancing environmental protection practices.