Organic fraction of municipal solid waste (OFMSW) is dominated by carbohydrates, including starch-based and lignocellulosic materials. The OFMSW was hydrothermally pretreated at 100–160 °C for 0–60 min, and then assessed for enzymatic ethanol production, followed by biogas production from the stillage. The highest glucose yield of 520 g/Kg of dry OFMSW, corresponding to 131% increase compared to that of the untreated OFMSW, was obtained after the pretreatment and enzymatic hydrolysis. Through ethanolic fermentation by an inhibitory tolerant fungus, Mucor indicus, 191.10 g ethanol/Kg of dry OFMSW was obtained, which was a 140.9% improvement in the ethanol yield compared to that from the untreated one. Methane production from the stillage (waste residues) resulted in 156 L/Kg OFMSW. In other words, a total of 10,774 KJ energy/Kg of dry OFMSW was generated at the best conditions.