The present invention relates generally to methods for enantiomeric separation of complex chemical mixtures using micelles of surfactant molecules that have a sulfate or sulfonate head group, a chiral selector, a linker, and a hydrophobic tail. Also provided are micelle compositions with sulfate or sulfonated head groups, methods of manufacture, and applications thereof. In particular, the micelles of the present invention provide an efficient enantiomeric separation and detection techniques for use in capillary electrophoresis and capillary electrophoresis with mass spectrometry.