AbstractElectron‐deficient aromatic ketones consisting of three fused anthraquinone units were synthesized by oxidation of the corresponding fused anthracenes. X‐ray analysis revealed that these compounds had nonplanar helical structures with unusual contacts, C=O⋅⋅⋅C=O 2.467 Å, between the inner carbonyl groups. The role of n⋅⋅⋅π* interactions in the short contacts was evaluated using a noncovalent interaction plot and natural bond orbital analysis. The dynamic process involving helical inversion was observed by the variable temperature 1H NMR measurement of a derivative with 2,4,6‐trimethylphenyl groups, and the barrier was estimated to be 77 kJ mol−1. DFT calculations indicated that the helical inversion proceeded via a multistep mechanism. The characteristic spectroscopic and electrochemical data due to the electron‐deficient anthraquinone units and the sterically congested carbonyl groups are discussed with the aid of DFT calculations.