The chromatographic selectivities of polystyrene-coated zirconia (PS- ZrO2) have been investigated in detail by means of homologue series retention studies and studies of a variety of nonpolar aromatic positional isomers. This material has been compared to polybutadiene-coated zirconia, octadecyl- and phenyl-bonded silica, and polymer-based reversed phases. In addition, the separations of a wide variety of compound classes on PS-ZrO2 were compared with those on other aromatic and aliphatic RPLC phases. The PS- ZrO2 material exhibits substantial differences in selectivity toward nonpolar and polar analytes as compared to other phases, especially with respect to polybutadiene-coated zirconia (PBD-ZrO2). On PS-ZrO2, polynuclear aromatic hydrocarbons (PAHs) are retained much more than are alkylbenzenes, whereas on PBD-ZrO2 the opposite is observed. In addition, PS-ZrO2 has much greater selectivity than does PBD-ZrO2 for the separation of structural isomers which differ in the position of phenyl groups. In general, even though the carbon content of PS-ZrO2 is much lower than that of conventional reversed-phase materials, such as octadecyl-bonded silica (C18-SiO2), polar analytes exhibit sufficient retention and differential selectivity on PS-ZrO2 that resolution comparable to that on C18-SiO2 can be obtained but with substantially improved analysis times.