Polybutadiene-coated zirconia (PBD-ZrO2) is very useful for reversed-phase separations under a wide variety of conditions. Its excellent chemical (pH = 1-13) and thermal (up to 150 °C) stability distinguish it from silica-based reversed phases. Just as with silica-based phases, zirconia's surface chemistry significantly influences the chromatography of certain classes of analytes. Zirconia's hard Lewis acid sites can be chromatographically problematic. Analytes such as carboxylic acids strongly interact with these sites on PBD-ZrO2 and do not elute. Addition of phosphate or other strong, hard Lewis bases to the eluent brings about elution, but the resulting peak is often tailed and broad. Typically, cationic solutes are more retained in the presence of phosphate or fluoride due to adsorption of the Lewis base additives and the concomitant development ora negative charge on the surface. This Coulombic interaction can be used to optimize selectivity, but the reversed-phase-cation-exchange retention can produce broad peaks with excessive retention. As an alternative to adding Lewis bases to the eluent, we studied the effect of permanently modifying PBD-ZrO2 by covalently attaching vinylphosphonic acid (VPA) to PBD which was predeposited in the pores of zirconia. We have investigated the chromatography of acids, bases, and small peptides on VPA-modified PBD-ZrO2 (VPA-PBDZrO2) and compared it to PBD-ZrO2. VPA-PBD-ZrO2 is a reversed-cation-exchange phase with properties quite different from PBD-ZrO2. The chemical stability of both phases led us to explore how low-pH (1.5-3), ultralow-pH (0), and high-pH (12) eluents effect the retention properties of these mixed-mode phases. Ultralow-pH eluents effectively separate small peptides on both phases. This approach gives lower retention, without sacrificing resolution, and much higher efficiency for small peptides than previously reported.