In the present work, the chromatographic behavior of the proline derivative captopril was studied on three different kinds of stationary phases. Four narrow-bore analytical columns were used in this study including particulate, monolithic, and two fused-core columns. The secondary equilibrium distribution of captopril and the peak shape were investigated at different mobile phase pH values and column temperatures. Under selected chromatographic conditions (pH: 2.5, 50 °C) where a single peak of captopril was obtained the performance of the studied narrow bore columns was compared.