1,4,5,8-Naphthalenetetracarboxylic dianhydride (NTCDA)-derived Polyimide is proposed as the anode material for aqueous rechargeable lithium-ion or sodium-ion battery (ARLB or ARSB), which is based on a mechanism beyond the intercalation chemistry. Comparing with other transient oxide anode for ARLB, Polyimide has more suitable working voltage, higher capacity and better structure stability. Therefore, the ARLB with Polyimide anode and LiCoO2 cathode presents a specific capacity of 71 mAh g−1 and a specific energy of 80 Wh kg−1 in 5 M LiNO3 solution at the current rate of 100 mA g−1, which is the highest among all reported ARLB system. Besides, it shows excellent cycling stability and rate capability. The ARSB system is demonstrated by Polyimide/NaVPO4F cell. It has been proved that the Polyimide anode has a good capacity performance and cycling stability in 5 M NaNO3 solution. The two aqueous rechargeable batteries with Polyimide anode both show a promising prospect in large-scale energy storage.