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Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N–O, CX (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C8H8) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C8–C4–C8(C16H12) and C8–C4–C8–C4–C8(C24H16) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C16H12and C24H16exhibit discharge capacities of 525.3 and 357.2 mA h g–1at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na+/Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C24H16-based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C4ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.