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Abstract We report a facile synthesis of diindeno‐fused dibenzo[a,h]anthracene derivatives (DIDBA‐2Cl,DIDBA‐2Ph, andDIDBA‐2H)with different degrees of non‐planarity using three substituents (chloro, phenyl, and hydrogen) of various sizes. The planarization of their cores, as evidenced by the decreased end‐to‐end torsional angles, was confirmed by X‐ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, which showed a transition from singlet open‐shell to closed‐shell configuration. Moreover, their doubly reduced states,DIDBA‐2Ph²⁻andDIDBA‐2H²⁻, were achieved by chemical reduction. The structures of dianions were identified by X‐ray crystallographic analysis, which elucidated that the electron charging further distorted the backbones. The electronic structure of the dianions was demonstrated by experimental and theoretical approaches, suggesting decreased energy gaps with larger non‐planarity, different from the neutral species.