A systematic study of the self-assembly process of a viologen-containing surfactant in aqueous medium is reported. Dodecyl-ethyl-viologendibromide (DDEV) is mixed in different proportions with dodecyltrimethylammonium bromide (DTAB), and the physicochemical properties of micellization are evaluated in order to find a suitable combination which does not interfere with the micellar properties of DTAB but introduces the characteristic properties of viologen. In this process, 1% doping of DDEV with DTAB was found to be the most appropriate, as negligible changes were observed in the physicochemical behavior of this system with respect to that of pure DTAB. The 1% DDEV-doped DTAB mixed micellar system showed the characteristic two-step reduction process for the viologen units at the interface as revealed by CV experiments. 1% mixing of DDEV with DTAB also allowed us to prepare stable w/o microemulsions containing viologen units at the interface which is otherwise unattainable with pure viologen surfactants. The charge-transfer capability of the viologen unit to the electron-rich 2,6-dihydroxynaphthalene (DHN) moiety inside the macrocyclic host, cucurbit[8]uril (CB[8]) is also evaluated for this system, and surprisingly even at this very low concentration, the ternary complex of DDEV-DHN@CB[8] transformed the micellar assembly to uniform vesicles. All of these properties have been further extended to other tetraalkylammonium surfactants, and similar effects were observed.