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Abstract Chemical reduction of pentacene (C₂₂H₁₄,1) with Group 1 metals ranging from Li to Cs revealed that1readily undergoes a two‐fold reduction to afford a doubly‐reduced1²⁻anion in THF. With the help of 18‐crown‐6 ether used as a secondary coordinating agent, five π‐complexes of1²⁻with different alkali metal counterions have been isolated and fully characterized. This series of complexes enables the first evaluation of alkali‐metal ion binding patterns and structural changes of the1²⁻dianion based on the crystallographically confirmed examples. The difference in coordination of the smallest Li⁺ion vs. heavier Group 1 congeners has been demonstrated. In addition, the use of benzo‐15‐crown‐5 in the reaction of1with Na metal allowed the isolation of the unique solvent‐separated ion product with a “naked” dianion,1²⁻. The detailed structural analyses of the series revealed the C−C bond alteration and core deformation of pentacene upon two‐fold reduction and complexation. The negative charge localization at the central six‐membered ring of1²⁻identified by theoretical calculations corroborates with the X‐ray crystallographic results. Subsequent in‐depth theoretical analysis provided a detailed description of changes in the electronic structure and aromaticity of pentacene upon reduction.