Highly efficient synthesis of benzyl benzoate directly from self-coupling of benzyl alcohol in water

•Benzyl benzoate (BB), an important fine chemical, is synthesized with a green catalytic system.•The system is highly efficient, with very high selectivity near full conversion in just 0.5 h.•The ester BB is produced directly from the self-coupling of benzyl alcohol.•The high catalytic efficiency is achieved by size regulation and proper functionalization of the support.•Reaction mechanism for the formation of BB is also put forward.