The cleanest form of energy, i.e., biohydrogen, and advanced biofuel, i.e., biobutanol, were produced from the organic fraction of municipal solid waste (OFMSW). Ethanol as a byproduct of this process was used for the pretreatment of this substrate, and this pretreatment was improved by other process byproducts, i.e., acetic acid and butyric acid. The pretreatment was conducted with 85% ethanol and 0-1% (w/w) acetic/butyric acid at 120 and 160 °C for 30 min. The pretreatment catalyzed by 1% (w/w) acetic acid at 120 °C resulted in a hydrolysate with 49.8 g/L total fermentable sugars, which was fermented to the highest overall yield of acetone, butanol, and ethanol (ABE) and hydrogen. Through this process, 114.1 g butanol, 43.8 g acetone, 15.1 g ethanol, 97.5 L hydrogen were obtained from each kg of OFMSW, producing 270 g ABE and 151 L H from each kg of substrate, corresponding to 6000 kJ energy production.