Industrial pollution has remained as one of the most daunting challenges for many regions around the world. Characterizing the determinants of industrial pollution should provide important management implications. Unfortunately, due to the absence of high-quality data, rather few studies have systematically examined the locational determinants using a geographical approach. This paper aimed to fill the gap by accessing the pollution source census dataset, which recorded the quantity of discharged wastes (waste water and solid waste) from 717 pollution-intensive firms within Huzhou City, China. Spatial exploratory analysis was applied to analyze the spatial dependency and local clusters of waste emissions. Results demonstrated that waste emissions presented significantly positive autocorrelation in space. The high-high hotspots generally concentrated towards the city boundary, while the low-low clusters approached the Taihu Lake. Their locational determinants were identified by spatial regression. In particular, firms near the city boundary and county road were prone to discharge more wastes. Lower waste emissions were more likely to be observed from firms with high proximity to freight transfer stations or the Taihu Lake. Dense populous districts saw more likelihood of solid waste emissions. Firms in the neighborhood of rivers exhibited higher waste water emissions. Besides, the control variables (firm size, ownership, operation time and industrial type) also exerted significant influence. The present methodology can be applicable to other areas, and further inform the industrial pollution control practices. Our study advanced the knowledge of determinants of emissions from pollution-intensive firms in urban areas.