The chiral resolving abilities of micellar solutions of four different bile salts alone and in mixtures with polyoxyethylene-4-dodecyl ether (C12E4) and methanol were investigated using MECC. The four bile salts investigated were the unconjugated sodium salts of cholic, deoxycholic, chenodeoxycholic and ursodeoxycholic acids. The test solutes included verapamil, norverapamil, gallopamil, bi-2-naphthol, atenolol and BAYK8644. The relative hydrophobicities of the micellar aggregates formed in solutions of binary mixtures of each bile salt with C12E4 were investigated by fluorescence spectroscopy using pyrene as a probe molecule. The observed enantiomeric resolution for the test compounds using these binary mixtures as MECC pseudo-stationary phases was determined. Correlations between micellar hydrophobicity for these solutions and chiral resolution of these test solutes are presented. The addition of C12E4 with or without methanol to solutions of sodium cholate and sodium deoxycholate enhanced the chiral resolution observed for compounds containing a longer hydrocarbon chain separating some of the major functional groups from the chiral center. The pure bile salt solutions generally provided better chiral resolution for the compounds where the major functional groups, such as aromatic rings, were closer to the chiral center.