A new anaerobic sequencing batch reactor (ASBR) unit with three stage concept was proposed and tested for spontaneous generation of hydrogen (H-2) and methane (CH4) from ethanol wastewater with maximum energy yield. The system was controlled at 37 degrees C, a fixed pH of 5.5 in the first bioreactor and a recycle ratio of unity from the third bioreactor to the first bioreactor to lower the amount of sodium hydroxide for pH regulation in the first bioreactor and to increase total alkalinity and process stability. Under the optimum organic loading rate of 15 kg COD/m(3)d (based on the total liquid holding volume), it exhibited the highest yields and specific generation rates of both gases, resulting in the uppermost overall energy yield which was much higher than those of all other anaerobic systems. The lactic acid was found to be about 4-8 times more toxic than acetic acid to methanogens. The higher the solution pH in any anaerobic system, the greater the reduction of micronutrients. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.