Molecularly imprinted, uniformly sized polymeric separation media were prepared using o-, m- or p-xylene as a porogenic template to investigate recognition ability towards coplanar polychlorinated biphenyls (PCBs). PCBs having chlorine atoms at meta positions of biphenyl were preferably retained on stationary phase with m-xylene as porogenic template and PCBs having chlorine atoms at para positions of biphenyl were found to be retained longer on the stationary phase imprinted by the porogenic template, p-xylene. It was found that positional relationship between substituted chlorine atoms was also important for chromatographic recognition.