Li-rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO2 and LiMn2O4; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high-energy lithium-ion batteries. Herein, hexagonal La0.8Sr0.2MnO3−y (LSM) is used as a protective and phase-compatible surface layer to stabilize the Li-rich layered Li1.2Ni0.13Co0.13Mn0.54O2 (LM) cathode material. The LSM is MnOMbonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM-coated LM delivers an enhanced reversible capacity of 202 mAh g−1at 1 C (260 mA g−1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g−1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next-generation of high-energy Li-ion batteries.