It has been well-documented that bile salts, including cholate and deoxycholate, can be used to form a pseudostationary phase in micellar electrokinetic capillary chromatography (MEKC) and employed for the separation of chiral isomers. However, despite many reports of bile salt micelles being used for chiral separations in chromatography and capillary electrophoresis, both the mechanism by which the micelle is formed from surfactant monomers and the molecular-level interactions between the isomers and the micelles are not well characterized. This work attempts to explore these two questions through careful and systematic characterization of both the MEKC behavior of model-drug analytes and nuclear magnetic resonance (NMR) signals obtained from the MEKC solutions. Using the model analytes 1,1'-binaphthyl-2,2'diyl hydrogenphosphate and 1,1'-binaphthyl as probes, we are able to closely examine the interactions between the micelle and chiral isomers and have begun to understand how the micelle and analytes interact. We also have further examined the interactions of bile salt monomers as they form micelles. The NMR examination of these aqueous MEKC systems has included 1H and 31P chemical shift analysis and, recently, 2D Nuclear Overhauser Effect Spectroscopy (NOESY). The data from the NMR experiments was correlated with MEKC results. We will present recent results from both MEKC and NMR that aid our increasing understanding of the complicated interactions between individual bile salt monomers, bile salt micelles and the analyte molecules.