Abstract Li-rich layered oxides have become one of the most concerned cathode materials for high-energy lithium-ion batteries, but they still suffer from poor cycling stability and detrimental voltage decay, especially at elevated temperature. Herein, we proposed a surface heterophase coating engineering based on amorphous/crystalline Li3PO4 to address these issues for Li-rich layered oxides via a facile wet chemical method. The heterophase coating layer combines the advantages of physical barrier effect achieved by amorphous Li3PO4 with facilitated Li+ diffusion stemmed from crystalline Li3PO4. Consequently, the modified Li1.2Ni0.2Mn0.6O2 delivers higher initial coulombic efficiency of 92% with enhanced cycling stability at 55 °C (192.9 mAh/g after 100 cycles at 1 C). More importantly, the intrinsic voltage decay has been inhibited as well, i.e. the average potential drop per cycle decreases from 5.96 mV to 2.99 mV. This surface heterophase coating engineering provides an effective strategy to enhance the high-temperature electrochemical performances of Li-rich layered oxides and guides the direction of surface modification strategies for cathode materials in the future.