Seven different reversed-phase (RP) stationary phases were examined under high-performance liquid chromatographic (pressure-driven, HPLC), and capillary electrochromatographic (electro-driven, CEC) conditions. Characterization of the stationary phases was performed following well-established test procedures providing a number of distinct column descriptors: hydrophobicity, hydrophobic selectivity and silanol activity. These parameters were used to describe the behavior of the RP-columns under both HPLC and CEC conditions. It is shown that chromatographic characteristics of porous RP-phases greatly depend on the mode of operation. By contrast, column descriptors of a non-porous viz. solid RP-phase material hardly differed for HPLC and CEC conditions.