The feasibility of simultaneous production of acetate and methane from glycerol was investigated by selective enrichment of hydrogenotrophic methanogens in an extreme-thermophilic (70. °C) fermentation. Fed-batch experiments showed acetate was produced at the concentration up to 13.0. g/L. A stable operation of the continuous stirred tank reactor (CSTR) was reached within 100. days. Acetate accounted for more than 90 w/w% of metabolites in the fermentation liquid. The yields of methane and acetate were close to the theoretical yields with 0.74-0.80. mol-methane/mol-glycerol and 0.63-0.70. mol-acetate/mol-glycerol. The obtained microbial community was characterized. Hydrogenotrophic methanogens, mainly Methanothermobacter thermautotrophicus formed 93% of the methanogenogenic community. This confirms that a high temperature (70. °C) could effectively select for hydrogenotrophic methanogenic archaea. Thermoanaerobacter spp. was the main bacterium forming 91.5% of the bacterial population. This work demonstrated the conversion of the byproduct of biodiesel production, glycerol, to acetate as a chemical and biogas for energy generation.