Rationally manipulating surface reconstruction of catalysts for water oxidation, inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges. Herein, the introduction of [Cr(C₂O₄)₃]³⁻ into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction (OER) activity. In view of the weak electronegativity of Cr³⁺ in [Cr(C₂O₄)₃]³⁻, the intercalation of [Cr(C₂O₄)₃]³⁻ is expected to result in an electron-rich structure of Fe sites in NiFe LDHs, and higher valence state of Ni can be formed with the charge transfer between Fe and Ni. The optimized electronic structure of NiFe-[Cr(C₂O₄)₃]³⁻-LDHs with more active Ni³⁺ species and the expedited dynamic generation of Ni³⁺(Fe)OOH phase during the OER process contributed to its excellent catalytic property, revealed by in situ X-ray absorption spectroscopy, Raman spectroscopy, and quasi-in situ X-ray photoelectron spectroscopy. With the modulated electronic structure of metal sites, NiFe-[Cr(C₂O₄)₃]³⁻-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm⁻². This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni³⁺ sites with the optimal electronic environment for improved OER electrocatalysis.