Electrochemical oxidation of reduced nicotinamide adenine dinucleotide (NADH) proceeds very effectively at 0.585 V versus Ag \ AgCl in pH 9.0 buffered solution at ambient temperature using ABTS(2-) (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) as an electron transfer mediator. The electrochemistry of ABTS(2-) and its oxidized form ABTS(.-), as well as the coupled homogeneous reactions were studied, and the rate constants were estimated using cyclic voltarnmetry and photometric methods (k(app,NADH) = 5.6-6.45 x 10(3) M-1 s(-1)). The mediated electrochemical oxidation was successfully coupled to horse liver alcohol dehydrogenase catalyzed oxidation of a meso-diol to a chiral lactone (yield 93.5%, ee > 99.5%).