Planar gliding along with anisotropic lattice strain of single‐crystalline nickel‐rich cathodes (SCNRC) at highly delithiated states will induce severe delamination cracking that seriously deteriorates LIBs’ cyclability. To address these issues, a novel lattice‐matched MgTiO3 (MTO) layer, which exhibits same lattice structure as Ni‐rich cathodes, is rationally constructed on single‐crystalline LiNi0.9Co0.05Mn0.05O2 (SC90) for ultrastable mechanical integrity. Intensive in/ex situ characterizations combined with theoretical calculations and finite element analysis suggest that the uniform MTO coating layer prevents direct contact between SC90 and organic electrolytes and enables rapid Li‐ion diffusion with depressed Li‐deficiency, thereby stabilizing the interfacial structure and accommodating the mechanical stress of SC90. More importantly, a superstructure is simultaneously formed in SC90, which can effectively alleviate the anisotropic lattice changes and decrease cation mobility during successive high‐voltage de/intercalation processes. Therefore, the as‐acquired MTO‐modified SC90 cathode displays desirable capacity retention and high‐voltage stability. When paired with commercial graphite anodes, the pouch‐type cells with the MTO‐modified SC90 can deliver a high capacity of 175.2 mAh g−1 with 89.8% capacity retention after 500 cycles. This lattice‐matching coating strategy demonstrate a highly effective pathway to maintain the structural and interfacial stability in electrode materials, which can be a pioneering breakthrough in commercialization of Ni‐rich cathodes. A lattice‐matched MTO coating has successfully been built on ultrahigh single‐crystal LiNi0.9Co0.05Mn0.05O2 particle by a neoteric in situ chemical reaction process, which can not only relieve lattice strain by avoiding inhomogeneity of the Li‐ion concentration, but also suppress cation mixing and irreversible oxygen loss for ensuring the smooth transportation of Li‐ion, thus preventing planar gliding and delamination cracking along the sliding planes.