Several surfactant systems were evaluated based on their system constants determined by the solvation parameter model for the design of a surrogate chromatographic model for the rapid estimation of octanol-water partition coefficient (log P o w ) by microemulsion electrokinetic chromatography. The system constant ratios responsible for the log P o w partition system are (nearly) the same as those for the microemulsion system containing sodium dodecyl sulfate (1.4% w/v), butan-1-ol (8% v/v) and heptane (1.2% v/v). Neutral and basic compounds are analyzed using a fused-silica capillary column with a 50 mM sodium phosphate-sodium borate (3:2) buffer at pH 10. Weakly acid compounds require the use of sulfonated silica capillary column and a 50 mM sodium phosphate buffer at pH 3. For 29 varied neutral and weakly basic compounds the average error between log P o w estimated using MEEKC and literature values was +/-0.12 over a log P o w range from 0.3 to 5.8.