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[Display omitted] • MIL-53(Fe)/metal (Ni, Co, Mn)-phenolic network nanoarchitectures were fabricated for OER. • MIL-53(Fe)/Ni-phenolic network nanoarchitectures revealed the best electrochemical performance due to interface effect. • This work supplied an efficient approach for water splitting. The interface nature of composite catalysts affected drastically the oxygen evolution reaction (OER) behavior. In this paper, nanoarchitecture consisted of Fe-based metal–organic frameworks (MIL-53) and metal-phenolic networks were created. Metal (Mn2+, Co2+, and Ni2+) phenolic networks were assembled on the surface of MIL-53 to form heterostructures. Among them, MIL-53(Fe)/Ni-phenolic network nanoarchitectures revealed the best electrochemical performance. The existence of MIL-53 enhanced the adsorption ability for OH− in the nanoarchitectures. The electron transfer between MIL-53 and Ni-phenolic networks adjusted the filling degree of e g orbitals to optimize the bonding strength between Fe3+/Ni2+ and oxygen intermediate species. MIL-53/Ni-phenolic networks nanoarchitectures exhibited well OER performance with a potential of 282 mV at 10 mA cm−2. This work provided an efficient insight into the structure-properties relation of a promising heterostructure catalyst for water splitting. [ABSTRACT FROM AUTHOR]