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The wide applications of rechargeable batteries require state‐of‐the‐art batteries that are sustainable (abundant resource), tolerant to high‐temperature operations, and excellent in delivering high capacity and long‐term cycling life. Due to the scarcity and uneven distribution of lithium, it is urgent to develop alternative rechargeable batteries. Herein, an organic compound, azobenzene‐4,4′‐dicarboxylic acid potassium salts (ADAPTS) is developed, with an azo group as the redox center for high performance potassium‐ion batteries (KIBs). The extended π‐conjugated structure in ADAPTS and surface reactions between ADAPTS and K‐ions enable the stable charge/discharge of K‐ion batteries even at high temperatures up to 60 °C. When operated at 50 °C, ADAPTS anode delivers a reversible capacity of 109 mAh g⁻¹at 1C for 400 cycles. A reversible capacity of 77 mAh g⁻¹is retained at 2C for 1000 cycles. At 60 °C, the ADAPTS‐based KIBs deliver a high capacity of 113 mAh g⁻¹with 81% capacity retention at 2C after 80 cycles. The exceptional electrochemical performance demonstrates that ADAPTS is a promising electrode material for high‐temperature KIBs.