Abstract The cyclic voltammetry (CV) measurements for the combinations of hexadecyltrimethylammonium bromide (HTAB), tetradecyltrimethylammonium bromide (TTAB), dimethylene bis(tetradecyldimethylammonium bromide) (14-2-14), and dimethylene bis(hexadecyldimethylammonium bromide) (16-2-16) with TritonX-100 (TX-100) and triblock polymer, Pluronic F68, have been carried out in the presence of 0.1 M KCl. The critical micelle concentrations of these binary mixtures over the whole mixing range have been determined by using electroactive probe 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). A variation in the various micellar parameters and diffusion coefficient of the electroactive probe indicates that the mixed micelle formation between the components of monomeric/dimeric and TX-100/F68 binary mixtures was synergistic in nature. The stronger synergistic interactions were observed for the cationic combinations with F68 rather than TX-100. The results have been discussed on the basis of reduction in the cationic polar head group repulsions by the intercalation of non-ionic surfactants in the mixed micelle.