Nine typical waste incinerating plants were investigated for polychlorinated naphthalene (PCN) contents in their stack gas. The incinerators investigated include those used to incinerate municipal solid, aviation, medical, and hazardous wastes including those encountered in cement kilns. PCNs were qualified and quantified by isotope dilution high resolution gas chromatography-high resolution mass spectrometry techniques. An unexpectedly high concentration of PCNs (13,000 ngNm −3 ) was found in the stack gas emitted from one waste incinerator. The PCN concentrations ranged from 97.6 to 874 ngNm −3 in the other waste incinerators. The PCN profiles were dominated by lower chlorinated homologues, with mono-to tetra-CNs being the main homologues present. Furthermore, the relationships between PCNs and other unintentional persistent organic pollutants involving polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls, hexachlorobenzene, and pentachlorobenzene were examined to ascertain the closeness or otherwise of their formation mechanisms. A good correlation was observed between ΣPCN (tetra-to octa-CN) and ΣPCDF (tetra-to octa-CDF) concentrations suggesting that a close relationship may exist between their formation mechanisms. The results would provide an improved understanding of PCN emissions from waste incinerators.