Seventeen soil samples collected in an industrial park located in Ningxia Province, Northwestern China were analyzed for polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs). The PCN, PCDD/F, and PCB concentration ranges were 183–3340, 7.00–215, and 45.1–355 pg/g, respectively. Positive matrix factorization showed that secondary ferrous metal smelters and cement kilns contributed more than 70% of the total PCN concentration. Historical use of Halowax 1051 also affected the PCN concentrations in soil. Principal component analysis indicated that the PCDD/F concentrations in soil in the study area were mainly affected by thermal processes in secondary ferrous metal smelters. CB-209 was an important contributor to total PCBs in the study area, and likely originated from the phthalocyanine-type pigments used in a local recycled paper mill. Samples S10, S1, S17, and S6 had high ∑TEQ (PCDD/Fs + PCNs + PCBs) concentrations, and the carcinogenic risks of PCDD/Fs, PCNs, and PCBs for workers from these samples were 0.487 × 10−6, 0.234 × 10−6, 0.230 × 10−6, and 0.210 × 10−6, respectively. According to our results, the health risks of PCDD/Fs, PCNs, and PCBs for workers in this area should be given more attention.