Irreversible phase transition and surface residual lithium, which cause the fast capacity fading of LiNi0.8Co0.1Mn0.1O2 (NCM811), are the main obstacles that hinder their commercial application. Herein, to modify the surface/interphase properties of NCM811, we elaborately propose a hybrid Li3PO4-AlPO4-Al(PO3)3 coating layer that combines the advantages of ionic conductor (Li3PO4) and thermal stable compound (AlPO4) via reacting aluminum metaphosphate (Al(PO3)3) precursor with the surface residual lithium (Li2CO3 or/and LiOH) during the coating process. When used as cathode for lithium-ion battery, the optimized NCM811 delivers a high initial discharge capacity of 201.8 mAh g−1 and 218.9 mAh g−1 at 0.1C under the temperature of 30 °C and 50 °C, with capacity retention of 85.4% and 78.89% after 50 cycles, respectively, which are much higher than that of uncoated sample (73.93% and 57.98%). Moreover, when it is coupled with graphite anode to form a lithium-ion full cell, it delivers an impressively high energy density of 467.5 Wh kg−1 (based on mass of positive and negative material), and retains 71.8% of its initial energy density after 100 cycles. The significantly enhanced electrochemical properties should be attributed to the multifunctional hybrid nano-coating layer that could efficiently reduce the surface residual lithium, suppress the irreversible phase transition, and prevent the active materials from the erosion of HF as verified by the ex-situ X-ray diffractometry, Raman spectroscopy and transmission electron microscopy. This work provides new insights into the surface/interphase design strategies to improve the structural stability of Ni-rich cathode, which will promote the development of high capacity cathode materials.