The paired electrolysis of acetone to produce diacetone alcohol (daa) under mild conditions (298 K, 1 atm) was explored. The results revealed that the main factors that affected the yield rate of daa were the coulombs of electricity passed, supporting electrolyte, amount of H2O, operating type, and current density, and that a minor factor affecting the yield rate of daa was the anode material. Under optimal conditions, no further condensation products other than daa in acetone self-condensation could be observed; i.e., the selectivity of daa was 100%, and the yield rate of daa was up to 850 g center dot F-1.