Electro-oxidative kinetic resolution of sec-alcohols mediated with a catalytic amount of an optically active N-oxyl was performed by use of a simple undivided cell under constant current conditions. The selectivity factor (S-value) increased remarkably when the reaction was performed at lower temperatures. The optically active N-oxyl was recovered and used repeatedly without any change in efficiency and selectivity. © 2000 Elsevier Science Ltd.