Display omitted The water oxidation process, which comprises the oxygen evolution reaction (OER), is a critical catalytic mechanism for sustainable technologies like water electrolysis and fuel cells. Herein, we develop a unique metal–organic framework aided vanadium pentoxide nanorods (MOF-V2O5 NRs-500) that can be used as an OER electrocatalyst under alkaline solutions. The crystal structure, surface chemical state, and porosity of MOF-V2O5 NRs-500 can be altered by annealing in an oxygen atmosphere. The resultant MOF-V2O5 NRs-500 demonstrate high catalytic activity against OER in basic conditions, with a low overpotential of 300 mV at a derived current density of 50 mA cm−2, and extraordinary durability of more than 50 h. Superior electrochemical performance might be attributed to the high exposure level of active sites emanating from porous MOF-V2O5 NRs-500. Furthermore, the porous MOF-V2O5 NRs-500 skeleton may provide homogenous mass transport channels as well as quick electron transfer.