Four coefficients are suggested to characterize the separation properties of separation electrolytes in MEKC. These coefficients are the electrophoretic mobility of the pseudostationary phase (PSP), the electroosmotic mobility and two parameters which can be obtained via the Martin equation using the retention data of the members of a suitable homologous series. These four coefficients are used for the characterization of separation electrolytes applicable to the separation of very hydrophobic analytes (log P-OW = 3-4) with SDS as PSP and to quantitatively describe the influence of the buffer additives ACN and urea for the fine-tuning of retention factors and the additive calcium chloride for the fine-tuning of the width of the migration time window. Together with carbon number equivalents (N-c(*)) as analyte descriptors the suggested coefficients provide a tool for the fast optimization of the composition of the separation electrolyte. The proposed method optimization scheme is applied to the separation of ingredients of essential oils. Predicted resolutions are compared to experimental results.