Occurrence of polycyclic aromatic hydrocarbons (PAHs) during the coking process has been widely recognized. The formation of polychlorinated naphthalenes (PCNs) from PAHs during some thermal related processes has been confirmed in many studies. Thus, the coking process is assumed to be a potential source of PCNs. However, intensive investigations on PCN emissions during the coking process are lacking. In order to evaluate PCN emissions from the coking process, an intensive study comprising 11 typical coke plants was undertaken. PCNs were qualified and quantified by isotope dilution HRGC/HRMS techniques. The concentrations of PCNs in stack gas samples collected from the investigated coke plants were in the range of 1.6-91.8 ng Nm(-3) (0.08-4.23 pg TEQ Nm(-3)). The emission factors of PCNs were found to be in the range of 0.77-1.24 ng TEQ per ton of coke production. The estimated annual toxic emissions of PCNs from the global coking industry vary from 430 to 692 mg TEQs. Characteristics of the PCN profiles were dominated by the lower chlorinated homologues, with mono-CN being the most abundant homologue. According to the PCN distribution and correlations of PCN homologues, it was speculated that chlorination is possibly the dominant pathway of PCN formation during the coking process.