To shed light on the mechanism of the enantioselective cobalta-electrocatalysis, a series of experiments were conducted. The kinetic isotope effect (KIE) experiment was performed by an intermolecular competition between substrates 1 and [D5]-1, and gave a product distribution value of 1.2 (PH/PD), which indicated that C-H bond cleavage might not be involved in the rate-determining step (Scheme 5A). We then intended the isolation of key chiral cobaltacycle intermediates. Due to instability of cobalt(III) intermediates, we prepared the cobalt(III) intermediates by introducing 4-methoxypyridine ligand. The cobalt(III) intermediate 45 was obtained from the reaction of benzamide with 1.0 equivalent of Co(OAc)2•4H2O, L3, NaOPiv, and 4-methoxypyridine in TFE/DCE (3:1, v/v, 4 mL) under electrolysis with a constant current at 1 mA. Likewise, the stoichiometric reaction of diarylphosphinic amides with 1.0 equivalent of Co(OAc)2•4H2O, L2, NaOPiv, and 4-methoxypyridine in TFE/H2O