The seasonal variation, source apportionment, and inhalation cancer risks of atmospheric polychlorinated naphthalenes (PCNs) were investigated in Ulsan, South Korea. Mean total concentrations of PCNs were 5.03 ± 3.78 pg/m3 in the gaseous phase and 0.29 ± 0.75 pg/m3 in the particulate phase. Tri-CNs (47%) and tetra-CNs (28%) predominated in the gaseous phase, whereas octa-CNs (68%) and hepta-CNs (17%) predominated in the particulate phase. Diagnostic ratios suggested that atmospheric PCNs were primarily influenced by combustion sources. Principal component analysis indicated that re-volatilization from Halowax-related sources was more pronounced in summer. Conditional bivariate probability function analysis revealed that elevated PCN concentrations in summer were driven by local industrial emissions. Concentration-weighted trajectory analysis indicated that long-range atmospheric transport (LRAT) contributed to particulate PCN concentrations during winter and spring, particularly for highly chlorinated congeners with greater toxicity. The annual inhalation cancer risk (1.8 × 10−8) was below the US EPA acceptable risk level. PCNs accounted for 17% of the annual total TEQs and up to 56% in summer when combined with other POPs from the national POP monitoring network. These results demonstrate that atmospheric PCNs from diverse sources, including industrial emissions, re-volatilization, and LRAT, can play an important role in dioxin-like toxicity in ambient air.