Defects have been found to enhance the electrocatalytic performance of NiFe-LDH for oxygen evolution reaction (OER). Nevertheless,their specific configuration and the role played in regulating the surface reconstruction of electrocatalysts remain ambiguous.H erein, cationic vacancy defects are generated via aprotic-solvent-solvation-induced leaking of metal cations from NiFe-LDH nanosheets.D FT calculation and in situ Raman spectroscopic observation both reveal that the as-generated cationic vacancy defects tend to exist as V M (M = Ni/Fe);under increasing applied voltage,they tend to assume the configuration V MOH ,a nd eventually transform into V MOH-H whichisthe most active yet most difficult to form thermodynamically.M eanwhile,w ith increasing voltage the surface crystalline Ni(OH) x in the NiFe-LDH is gradually converted into disordered status;u nder sufficiently high voltage when oxygen bubbles start to evolve,l ocal NiOOH species become appearing,w hich is the residual product from the formation of vacancy V MOH-H .T hus,w ed emonstrate that the cationic defects evolve along with increasing applied voltage (V M ! V MOH ! V MOH-H ), and reveal the essential motif for the surface restructuration process of NiFe-LDH (crystalline Ni(OH) x ! disordered Ni(OH) x ! NiOOH). Our work provides insight into defect-induced surface restructuration behaviors of NiFe-LDH as at ypical precatalyst for efficient OER electrocatalysis.