Two novel redox-active organic cathodes PPTO and PEPTO have been developed. The replacement of a single C–C bond (in PPTO) with a carbon–carbon (CC) triple bond (in PEPTO) could greatly enhance the performance of organic cathodes. As a result, PEPTO delivers a significantly improved rate stability at high current densities and an excellent capacity retention of 110 mA h g⁻¹ after 1000 cycles.