The retention of 13 steroidal drugs was determined on a polyethylene-coated silica column using methanol-water mixtures at various organic phase concentrations. Good linear relationships were found between the log k' values and the organic mobile phase concentration in the eluent. The slope and intercept values of the relationships were correlated with the physicochemical parameters of the steroidal drugs by means of canonical correlation analysis. Calculation proved that the retention characteristics significantly depend on the physicochemical parameters of the solute. The electronic parameters exerted a higher impact on the retention than the hydrophobicity did. This result, is probably due to the hydrophobic interactions between the polar substructures of drugs and the free silanol groups not covered by the hydrophobic ligand.