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Organic electrode materials could revolutionize batteries because of their high energy densities, the use of Earth‐abundant elements, and structural diversity which allows fine‐tuning of electrochemical properties. However, small organic molecules and intermediates formed during their redox cycling in lithium‐ion batteries (LIBs) have high solubility in organic electrolytes, leading to rapid decay of cycling performance. We report the use of three cyclotetrabenzil octaketone macrocycles as cathode materials for LIBs. The rigid and insoluble naphthalene‐based cyclotetrabenzil reversibly accepts eight electrons in a two‐step process with a specific capacity of 279 mAh g−1 and a stable cycling performance with ≈65 % capacity retention after 135 cycles. DFT calculations indicate that its reduction increases both ring strain and ring rigidity, as demonstrated by computed high distortion energies, repulsive regions in NCI plots, and close [C⋅⋅⋅C] contacts between the naphthalenes. This work highlights the importance of shape‐persistency and ring strain in the design of redox‐active macrocycles that maintain very low solubility in various redox states. [ABSTRACT FROM AUTHOR]