It was newly found that the electrodes modified by applying ethanol solutions of Nationcontaining os(bpy)32+ onto the substrate electrode (the one-step method) show two pairs of stableredox peaks of Os(bpy)32+/3+ on cyclic voltammogram near 0.54V and 0.25V, respectively. Thesemoditied electrodes can effectively mediate and catalyze the first and second steps of nitritereduction in acidic media in the potential region 0-0.9V when the loading in the coating (X=F(Os2+) / F(SO3-)) and pH in solution are below 0. 17 and 4, respectively. When X is between 0.33and 0. 17. only the current peak near 0.54V appears regardless of solution pH and only the first stepof NO2 reduction is catalyzed. Thus the modified electrode provides a very useful flexibility thatone can control the reaction pathway and catalytic activity of nitrite reduction by simply changingthe concentration of the mediator in the coating.