The transition from vesicles to micelles by adding octane into the dodecyl-pyridinium chloride (DPC1)/sodium laurate (SL), and dodecyltrimethylammonium bromide (DTAB)/SL aqueous two-phase systems has been studied. The two-phase systems were transformed into single-phase isotropic solutions with the addition of a certain amount of octane. The results of dynamic light scattering (DLS) demonstrate the decrease of large aggregates (vesicles) and the increase of the small aggregates (spherical micelles) upon octane addition. Such transformation of the surfactant aggregates was also corroborated by the results of time-resolved fluorescence quenching (TRFQ) and viscometry. The change of the phase behavior was discussed on the basis of the interaggregate interactions influenced by the variation of organized assemblies.