Ni-rich layered oxides are considered promising cathodes for advanced lithium-ion batteries (LIBs) in the future, owing to their high capacity and low cost. However, the issues on structural and interfacial stability of Ni-rich cathodes still pose substantial obstacles in the practical application of advanced LIBs. Here, we employ a one-step method to synthesize a B-doped and La4NiLiO8-coated LiNi0.825Co0.115Mn0.06O2 (BL-1) cathode with reliable structure and interface, for the first time. The La4NiLiO8 coating layer can prevent cathodes from electrolyte assault and facilitate Li+ diffusion kinetics. Moreover, B-doping can effectively restrain the pernicious H2-H3 phase transition and adjust the orientation of primary particles to a radial alignment, which is obstructive to the arise of microcracks induced by the change of anisotropic volume. Specifically, when tested in pouch cells, the BL-1cathode exhibits outstanding capacity retention of 93.49% after 500 cycles at 1C. This dual-modification strategy dramatically enhances the stability of the structure and interface for Ni-rich cathode materials, consequently accelerating the commercialization process of high-energy–density LIBs.