Technical toxaphene and a 22-component Reference Mixture were analyzed using capillary gas chromatography with split/splitless injection (SSL) and on-column injection (OC). In both techniques, electron-capture, negative ionization mass spectrometry (ECNI-MS) was used for detection of chlorobornanes, chlorocamphenes and related compounds. Significant discrimination of highly chlorinated congeners was observed as a result of incomplete transfer of these compounds from the vaporizer to the analytical column when using SSL. This resulted in a much lower response for nona- and decachloro congeners than when using OC. In addition, several toxaphene components, especially the chlorobornanes with gem dichloro substitution on the six-member carbon ring, undergo thermal degradation when using SSL. Some of these congeners are major components of technical toxaphene, but generally are not present, except at low concentrations, in environmental and biological samples. Therefore, technical toxaphene may be discriminated and/or degraded differently than toxaphene compounds in environmental samples when using SSL. This results in significant bias of the quantitative data when using the technical material as a reference. OC suffers much less from these deficiencies and, therefore, is a preferable technique for toxaphene analysis.