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The effect of pH regulation in phase I on hydrolysis and acidogenesis rate, metabolites production, microbial community, and the overall energy recovery efficiency during two‐phase anaerobic digestion (AD) of food waste (FW) was investigated. pH strongly affected the acidogenesis rate and the yield of the fermentation products. The highest acidogenesis efficiency (60.4%) and total volatile fatty acids (VFA)/ethanol concentration (12.4 g/L) were obtained at pH 8 during phase I. Microbial community analysis revealed that Clostridium IV was enriched at pH 8, relating to the accumulation of butyrate. Also, Clostridium sensu stricto played a crucial role in hydrogen production and was abundant at pH 6, resulting in the highest hydrogen yield (212.2 ml/g VS). In phase II, the highest cumulative methane yield (412.6 ml/g VS) was obtained at pH 8. By considering the hydrogen and methane production stages, the highest energy yield (22.8 kJ/g VS, corresponding to a 76.4% recovery efficiency) was generated at pH 8, which indicates that pH 8 was optimal for energy recovery during two‐phase AD of FW. Overall, the results demonstrated the possibility of increasing the energy recovery from FW by regulating the pH in the hydrolysis/acidogenesis phase based on the two‐phase AD system. Practitioner points: pH 8 was suitable for hydrolysis, acidogenesis, and methanogenesis.High hydrogen yields were obtained at pH 5–8 (about 200 ml/d).Clostridium sensu stricto might have played a crucial role in hydrogen production.High methane production (about 400 ml/g VS) was obtained at pH 7–9.pH 8 was optimal for energy recovery from FW with an efficiency of 76.4% (22.8 kJ/g VS). [ABSTRACT FROM AUTHOR]