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In this letter, high-performance polyimide (PI)-based resistive random access memory (ReRAM) is presented by utilizing a new DAXIN-PI thin film as a resistance layer. The switching between highand low-resistance states is triggered by the formation and dissociation of the charge transfer complex. As compared with the electrochemical-metallization-based ReRAM and the valence-change-based ReRAM, this DAXIN-PI ReRAM shows excellent performance, including large Ron/Roff ratio, superior endurance, low operation voltage, fast switching speed, needless of a forming process, and acceptable retention characteristics. Among them, large Ron/Roff ratio (>; 105) and superior endurance (>; 105 cycles) can be simultaneously achieved, and the detailed reliability test for PI-based ReRAMs has been analyzed for the first time.