Cyclic voltammetry and controlled-potential electrolysis have been employed to investigate and characterize the reductive intramolecular cyclization of ethyl 2-bromo-3-(3',4'-dimethoxyphenyl)-3-(propargyloxy)propanoate (1) promoted by (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)nickel(I), [Ni(tmc)](+), electrogenerated at glassy carbon cathodes in dimethylformamide containing tetraalkylammonium salts. Cyclic voltammograms for reduction of [Ni(tmc)](2+) in the presence of 1 reveal that [Ni(tmc)](+) catalytically reduces 1 at potentials more positive than those required for direct reduction of 1. During controlled-potential electrolyses of solutions containing [Ni(tmc)](2+) and 1, catalytic reduction of the latter proceeds via one-electron cleavage of the carbon-bromine bond to form a radical intermediate that undergoes cyclization to afford 2-(3',4'-dimethoxyphenyl)-3-(ethoxycarbonyl)-4-methylenetetrahydrofuran (2). In the presence of a base (either electrogenerated or deliberately added as potassium tert-butoxide), 2 rearranges to give 2-(3',4'-dimethoxyphenyl)-3-(ethoxycarbonyl)-4-methyl-2,5-dihydrofuran (3). A mechanistic scheme is proposed to explain the results obtained by means of cyclic voltammetry and controlled-potential electrolysis.