MEKC and linear solvation free energy relationships (LSFERs) have been used to characterize the solute distribution between water and self-assemblies formed from ionic liquid type mono-chain cationic surfactants containing a cyclic pyrrolidinium head group. Several features of the solvation environment afforded by these micellar solutions were found to be quite different from that of CTAB, a structurally analogous cationic surfactant with a conventional, acyclic quaternary ammonium head group. None of the LSFER coefficients were found to vary in any systematic way with increasing alkyl chain length for these unique surfactants. Overall, however, these surfactants display different behavior than do all known cationic detergents such as CTAB. In chemical terms, pseudo-phases formed by these N-alkyl-N-methylpyrrolidinium bromides interact more strongly with polar compounds and less strongly with compounds having nonbonding or pi-electrons and are more cohesive compared to the well-studied CTAB.