Involving more nickel proportion in Ni-rich cathodes, edging to LiNiO₂, is an inevitable trend to satisfy the demand of high energy density in lithium-ion batteries, but an inducement for the severer formation of undesirable lithium residues. To overcome the consequent degradation behaviors, a LiCoO₂@Co₃O₄ complex coating layer is successfully realized on the surface of LiNiO₂ via a facile wet-chemical method taking advantage of the Li-reactive ability of Co₃O₄. As a result, the 0.4 wt.% Co modified material exhibits competitively enhanced cyclic performance with 178.1 mAh g⁻¹ after 50 cycles at 1 C, 11% higher than the pristine one in retention rate. Even at higher rates and temperature, it shows better electrochemical stability as well. The superior electrochemical properties of LiCoO₂@Co₃O₄ coated LiNiO₂ is ascribed to the dual-function of the coating method, where Co₃O₄ is formed during heat treatment and simultaneously reacted with surface lithium residues to generate LiCoO₂. In combination of bulk and surface characterization, the significant effects of the coating layer on stabilizing material interface and strengthening the kinetic characteristics for LiNiO₂ cathode materials are investigated and elucidated in detail.