Achieving a metabolic balance between volatile fatty acid (VFA) production and conversion is a standing challenge in high temperature and organic loading rate anaerobic digestion. A thermophilic anaerobic digestion reactor fed with food waste was therefore operated for 230 days to investigate metabolic performance in acidogenesis and methanogenesis. Results showed a methane yield of 310 mL/g·COD under an organic loading rate (OLR) of 10.0 kg·COD/(m3·d). The VFA concentration of 110 mg/L was low, indicating well-balanced VFA production and conversion metabolism. Highly specific acetic acid and propionic acid methanogenic activity showed satisfactory metabolic capability. Methanosarcina (95.2%) predominated in the high OLR state and increased abundance of Methanothermobactger (4.2%) was also observed. Syntrophic acetic acid oxidation bacterial was not found in different HRT conditions. It is therefore reasonable to speculate cleavage of acetic acid by mixotrophic Methanosarcina. Good acidogenesis and methanogenesis balance promote stable thermophilic AD of food waste under a high OLR.