Carbon nanotubes (CNTs) have demonstrated outstanding chemical and mechanical stability, electrical properties, and strong interactions with aromatic compounds owing to the p-electron system on the graphene sheets. Taking advantage of these unique properties, we have developed a fully validated sample pre-concentration technique for determination of polychlorinated biphenyls (PCBs) in aqueous environments using gas chromatography combined with a micro-cell electron capture detector (GC-mECD). The optimized method using pristine MWCNTs gave recoveries in the range of 46.0-92.5%, 51.4-91.5%, 48.7-77.8% for tap water, river water, and lake water, respectively. Compared to conventional C18 adsorbent and oxidized MWCNTs (oMWCNTs), pristine MWCNTs provided the best recoveries, thereby confirming that MWCNTs are excellent alternatives for C18, with the ability to achieve high performance. The developed protocol achieved method detection limits in the range of 0.002-0.011 mg L À1 and relative standard deviation (RSD) < 15.5%.