We proposed a new electrochemical strategy to characterize the hydrophobic microenvironment of micellar-hybridized supramolecular gels. The micellar-hybridized systems consist of micelles formed from gemini surfactants and supramolecular gels formed by self-assembly of the gelator N,N-dibenzoyl-L-cystine (DBC). SEM images indicated that the microscopic morphology of micellar-hybridized DBC gels possessed a denser three-dimensional network structure. An important feature of micellar-hybridized supramolecular gels is the presence of hydrophobic microdomains within the systems. The interaction of Methylene Blue (MB) and the hydrophobic microdomains can be quantitatively characterized by the net positive shifts of the redox formal potential (E-0') and the change of peak currents (i(p)) obtained from the cyclic voltammograms of MB. Delta E-0' between the micellar-hybridized DBC gel and non-hybridized gel was much larger than that between the micellar solution and aqueous solution, implying that the alteration of hydrophobicity of microdomains in hybrid system. By comparing the apparent diffusion coefficients of MB in the varied systems, it is indicative that the apparent diffusion coefficients of MB can be also employed to characterize the hydrophobicity change of hybrid systems. The fluorescent spectra of 1,8-anilinonaphthalenesulfonic acid within the hybrid gels further verified the results of the cyclic voltammograms. It is suggested that the cyclic voltammograms are a facile and sensitive method to monitor the hydrophobic microenvironment of the micellar-hybridized supramolecular gels. (C) 2012 Elsevier Ltd. All rights reserved.