Recent advances in the analysis of the chlorinated environmental pollutants polychlorinated naphthalenes (PCNs) and toxaphene are highlighted in this review. Method improvements have been realized for PCNs over the past decade in isomer-specific quantification, peak resolution, and the availability of mass-labeled standards. Toxaphene method advancements include the application of new capillary gas chromatographic (GC) stationary phases, mass spectrometry (MS), especially ion trap MS, and the availability of Standard Reference Materials that are value-assigned for total toxaphene and selected congener concentrations. An area of promise for the separation of complex mixtures such as PCNs and toxaphene is the development of multidimensional GC techniques. The need for continued advancements and efficiencies in the analysis of contaminants such as PCNs and toxaphene remains as monitoring requirements for these compound classes are established under international agreements.