In solid-support-free liquid-liquid chromatography, both phases can be used as a mobile phase and, moreover, their role and flow direction can be reversed during the course of the separation. This is the background of the concept of sequential centrifugal partition chromatography (sCPC) developed to perform a continuous separation in a cyclic manner. The feed is continuously introduced between two centrifugal partition chromatographic columns and two products are alternately collected at the opposite ends of the columns. In this work, a method is presented to select the operating parameters of an sCPC unit for the complete separation of a binary feed mixture. The method uses, as a basis, a restricted number of experiments needed to determine the distribution equilibrium of the components to be separated and to evaluate the column hydrodynamics. The method was validated experimentally for the separation of a binary mixture of hydroquinone and pyrocatechol.