Recently, Co-free Ni-rich cathodes have received extensive concerns as a competitive candidate for next-generation sustainable lithium-ion batteries (LIBs) due to their high-capacity/operation voltage merits and elimination of expensive Co component. However, it is extremely challenging to solve the issues involving their intrinsic chemo-mechanical instabilities triggered by anisotropic lattice stress and short cycle life. Herein, we rationally incorporate tiny quintuple high-valence cations to engineer an entropy-assisted LiNi