Cyclic voltammetry has been employed to investigate the mixed micellar behavior of the binary Mixtures of different zwitterionic surfactants Such as 3-(N.N-dimethylhexadecylammonio)propane sulfonate (HPS), 3-(N,N-dimethyltetradecylammonio)propane sulfonate (11,S) and 3-(N,N-dimethylcloclecylammonio)propane sulfonate (DPS) with three triblock polymers (L64, F127 and P65) by using 2,2,6,6-tetrametliyl-1-piperidinyloxy (TEMPO) as an electroactive probe at 25 degrees C. Critical micellar concentration (cmc) has been determined from the plots of variation in peak current (i(p)) versus the total concentration of surfactant/triblock polymer. Diffusion coefficient of the electroactive species has also been reported. The regular solution theory approximation has been used to determine various micellar parameters of ideal systems. The variation in micellar mole fraction (XI) of the zwitterionic surfactant supports the formation of mixed micelles, which are rich in triblock polymer component in the surfactant rich region of the mixture and vice versa. The regular solution interaction parameter (0) suggests the formation of mixed micelles due to the synergistic interactions in case of Hps/TPS/DPS + F127/P65 systems and gets affected by EO/PO ratio of triblock polymers. (C) 2008 Elsevier Inc. All rights reserved.