Chiral polymeric surfactants, also known as micelle polymers, have been developed over the past decade for use as chiral selectors in the analytical separation of enantiomers. In this study, fluorescence spectroscopy and pulsed field gradient NMR (PFG-NMR) were used to determine how the concentration at which the micelles were polymerized affects their size and structure. Ten different polymerization concentrations of sodium N-undecanoyl-L-valinate (L-SUV) were investigated, ranging from slightly below the critical micelle concentration (cmc) to 50 times greater than the cmc. Analysis of fluorescence probe data indicates that significant changes in the micropolarity and microviscosity of the polymer occurred as a function of the polymerization concentration. Pulsed field gradient NMR and fluorescence quenching were also used to investigate the changes in the size of the polymers as a result of the polymerization concentration. In addition, PFG-NMR revealed information concerning the polydispersity of the micelle polymers, which is a crucial factor in understanding the chiral interactions of these species.