A rapid method for the determination of lipophilicity by reversed-phase high-performance liquid chromatography is presented with a study of a set of 29 molecules representing various functional groups. The use of a short column packed with a polar-embedded phase and octanol-saturated water as eluent for direct measurement of log k(w) is described. Extrapolation for log k(w) measurements can be avoided for solutes having log P in the octanol/water system of less than 3.2. The gain in terms of productivity and simplicity of analysis over the direct measurement shows the usefulness of this method for industrial applications. Good correlations between log P values found in the literature and measured log k(w) values were obtained.