Upon electrochemical oxidation of configurationally stable biphenyl-based electron donors (R-ax)-1a and -1b to butane-1,4-diyl dications (M)-2a(2+) and -2b(2+), drastic changes were induced not only in UV-vis but also in CD spectra. Because of the hydrophilic oligoethylene glycol units on the amino nitrogens, (R-ax)-1b and (M)-2b(2+) are soluble in water, thus realizing the electrochiroptical behavior not only in organic solvents but also in aqueous media.