The feasibility of six ionic liquid- (IL-) based stationary phases for the analysis of environmentally important polychlorinated biphenyls (PCBs) by gas chromatography combined with either electron capture micro-detector (GC-micro-ECD) or quadrupole mass spectrometry (GC-MS, for confirmation) have been evaluated. These IL-based columns showed a separation mechanism different from that observed for other commercial phases, such a low bleed high temperature 8% phenyl (equiv.) polycarborane-siloxane suggested shape-selective phase for non-ortho and mono-ortho-CBs, HT-8, or a polar poly(ethylene glycol), resulting in a different elution order of the 69 investigated PCBs. However, no all phases provided equality satisfactory resolutions for the most environmentally relevant congeners, the 12 toxic and the 7 priority PCBs. From this point of view, the best results were obtained with the SLB-IL76 and SLB-IL59 phases, which showed a number of coelutions for these specific congeners only slightly higher to that observed on HT-8. Interestingly, the SLB-IL59 phase was the only one among the evaluated phases allowing a complete resolution of the most toxic non-ortho substituted congeners # 77, 126 and 169 from all other PCBs investigated. SLB-IL76 and SLB-IL59 also demonstrated a superior chromatographic performance concerning peak symetry, retention time stability and column bleeding, compared to the other four IL-based columns evaluated. Altogether, results obtained for the analysis of pure standards illustrated the potential of, in particular, SLB-IL 59 as an alternative phase for confirmation of the identity of PCBs typically detected in environmental matrices that coeluted on conventional non-polar phases in use for this type of determination. However, the long-term stability and quantitative behaviour of these stationary phases during the analysis of real samples still need to be addressed.