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In this service, capillary electrophoresis was applied to investigate the chiral recognition mechanism for the enantioseparation on a well-known second-generation photodynamic therapy drug of benzoporphyrin derivative monoacid ring A, that is, verteporfin. Cholate salts have been studied as the chiral selectors, which can realize baseline separation of the four verteporfin isomers. The analytes selectively combine with the chiral micelles, that is, dynamic H-bonds interactions occur between the hydroxyl groups on the outer side of the cholate micelles and the ester/carboxy groups of the four isomers.