Representative 1,2‐diactivated olefins , in which X and Y are electron‐withdrawing groups not themselves reduced in the course of the electrolyses, were studied in polarography, cyclic voltammetry, electron spin resonance spectroscopy, and macroelectrolyses. This first of three papers deals with the voltammetry of these compounds and the evidence it affords that a major pathway to the cathodic formation of reduced dimeric products at the first reduction wave is the nucleophilic attack of the intermediate anion radical on starting material rather than radical dimerization of the anion radicals. The rates of disappearance of the anion radicals were measured as a function of olefin concentration as well as the concentration of proton source and Michael‐type acceptor. In each case a linear dependence of observed rate on concentration was noted. The implications for directed synthesis and for anionic polymerization are discussed.