An interesting sequence of oxidation/Michael addition/oxidation/spirocyclization is observed in the electrolysis of caffeic acid esters in the presence of barbituric acid derivatives leading to the synthesis of a series of novel spirocycles. In an experimentally simple and clean procedure, the electrolyses proceed via a domino of electrochemical (E) and chemical (C) events with employing electrons as the only reagents in aqueous solution without introducing any catalyst or oxidant. From mechanistic point of view, a new type of domino mechanism (ECECi, C-i = spirocyclization) is proven with a unique C-i phenomenon at final step. Also, in light of experimental and theoretical NMR investigations, highly chemo and regioselectivities have been detected in these synthetic electrolyses. (C) 2015 Elsevier Ltd. All rights reserved.