For aqueous rechargeable lithium battery (ARLB), excellent cycling stability at elevated temperature is highly desirable in its application of electric vehicles (EVs). However, most state-of-art ARLBs show poor durability under high-temperature operation. Herein, we demonstrate a facile coating approach that can construct a thin acrylonitrile copolymer (ANC)/graphene skin on the top-surface of the LiMn2O4 (LMO) cathode in a rechargeable hybrid aqueous lithium battery (ReHAB). Featuring the continuous coverage and the facile electron transport, the ANC/graphene skinned cathode shows a capacity retention of 61% after 300 cycles at 60 °C, two times larger than the battery without the skin. In the cathode, ANC helps to suppress unwanted interfacial side reactions, and graphene renders a robust ion diffusion framework. Quantitative analysis of Mn suggests that the ANC/graphene skin can greatly suppress dissolution of Mn from the LMO into the aqueous electrolyte, while maintaining the charge transfer kinetics. The polymer-based nanocomposite skin on small (1.15 mAh cell) and large (7 mAh cell) cathodes show similar electrochemical improvement, indicting good scale-up potentials.