Because of their special features, NiFe-LDHs (nickel iron layered double hydroxides) are prospective OER (oxygen evolution reaction) catalysts that might be utilized to catalyse the electrolysis of water and produce hydrogen to address the energy crisis. In this work, the electronic structure and electrocatalytic performance of the NiFe-LDH were accurately regulated by optimizing the Ni sites, which was enabled by adjacent metal sites coordinated with the "polyoxometalate electron sponge". With extension of the modification time, the Ni 2p binding energy, the Ni 3+ /Ni 2+ ratio and the OER properties were gradually tuned, which indicated accurate regulation of active Ni sites by the "polyoxometalate electron sponge" on a temporal scale. Additionally, NiFe-LDH-PW 12 -12 h (NiFe-LDH modified by polyoxometalate anions for 12 h) showed the highest OER performance along with fast electron transfer, superior reaction kinetics and electrochemical durability, with an overpotential ∼68 mV lower than that of NiFe-LDH. This work provides an accurate strategy for regulating the electronic structures of active metal sites for the OER.