Lipophilicity and methylene selectivity of mixed pseudo-stationary phases (PSPs) (containing lithium dodecyl sulphate (LDS) and lithium perfluorooctanesulphonate (LiPFOS) in different molar ratios) applied in MEKC have been investigated. Micellar proportion (t(prop,mic), a quantity expressing that how much time is spent by the analyte in the micellar phase related to its whole migration time), CLOGP(50) value (showing the value of hydrophobicity of a molecule spending exactly 50% of its migration time in the PSP) and methylene selectivity have been determined for different LDS/LiPFOS mixed phases. Values of the above-mentioned parameters have been determined for analytes with different chemical structures (alkylbenzene and alkylphenone homologous series, alcohols). Good linear correlation was obtained between either the micellar proportion, CLOGP(50), or methylene selectivity and the phase composition for the mixed phases. Lipophilicity and methylene selectivity of the mixed LDS/LiPFOS PSPs can be calculated and can continuously be changed by mixing the two single phases (LDS and LiPFOS) in the appropriate (and calculable) portion.