MEKC and the linear solvation energy relationship (LSER) model have been applied to two series of cationic surfactants. The synthetic flexibility of the quaternary ammonium group is exploited to generate the two series, one consisting of linear substitutions and the other incorporating the ammonium into ring structures of varying size. The effects of the head group structure on the CMC, aggregation number, and electrophoretic properties of the surfactants were determined. These surfactants were also characterized with the LSER model, which allowed the contributions of five chemical factors to the interactions between solutes and the micelles to be evaluated. Trends were observed in the cohesivity and polarity of the linear surfactant series, with both increasing with the size of the head group. No trends in the LSER parameters were observed in the cyclic series, but the LSER results do show that the surfactants with cyclic head groups provide a significantly different solvation environment from the linear series. Additional trends were observed in the aggregation behavior and chromatographic properties of the surfactants. These included changes in the CMCs, aggregation numbers, EOF, and electrophoretic mobility of the micelles that correlate to changes in head group size.