Amphipathic viologen, 1-ethyl-1'-cetyl-4,4'-bipyridinium dibromide (C/sub 16/C/sub 2/V/sup 2 +/), formed micelles in aqueous solution at concentrations above 8 x 10/sup -4/ M. /sup 1/H NMR chemical shifts of the bipyridinium moiety were in good agreement with a spherical micelle model, where the axis of the bipyridinium group is oriented perpendicular to the surface. Electron exchange between C/sub 16/C/sub 2/V/sup 2 +/ and C/sub 16/C/sub 2/V/sup +/ was studied by an ESR method in cetyltrimethylammonium chloride (CTAC)-C/sub 16/C/sub 2/C/sup 2 +/ mixed micellar systems. Extensive broadening of the ESR spectra was observed with increasing C/sub 16/C/sub 2/V/sup 2 +/ fraction, which indicated electron migration by exchange on the micellar surface.