Coal chemical industry (CCI) sites are characterized by complex environmental media, combined heavy metal pollution, and diverse exposure routes. However, existing human health risk assessment (HHRA) methods have multiple drawbacks, such as their small scope of application, limited assessment factors, and insufficient case applications. After 128 soil samples were collected, the contents of Be, V, Ni, Cu, Zn, As, Cd and Hg in the soils were analyzed based on general risk assessment guideline of China. Then, risk levels were calculated based on oral ingestion, skin contact and inhalation as the main exposure routes to compare and screen priority heavy metals. Furthermore, control values were identified through a contribution rate calculation model when CR > 10−6 or HQ > 1. As reference values, risk thresholds were proposed for heavy metals, and then a soil HHRA framework for the CCI site was constructed. Under the three exposure routes, the total CR was As > 10−6, and the total HQ was 1 > As > Cd; the HHRs related to As and V via the oral ingestion, dermal contact, and inhalation pathways were 76.67%, 13.13%, and 10.18% and 1.66%, 0, and 98.34%, respectively. The risk control value of As was 1.59 mg/kg and that of V was 25.1 mg/kg. Based on these results, the threshold values for priority heavy metals should be based on comprehensive considerations of the elemental background of a specific area, the contaminant criteria in different areas, the regional industrial development plan, and the most important control criterion, as well as the control value. Through the development of an HHRA framework and case verification, the authors of this article aim to guide CCI managers in screening priority heavy metals, formulating protection measures, developing improved operational procedures and improving the HHRA system for polluted CCI sites.