Crystal structures of alkali salts of tetrahaolgenosemiquinone anion radical acetone solvates and their solvent-free salts are determined. p-Semiquinone anion radical reveals enhanced aromaticity of the ring compared to the quinone. A pair of π-stacked radical anion (p-semiquinone) rings occurs in crystal structures of potassium and rubidium salts of tetrachlorosemiquinone anion acetone solvates and their potassium tetrabromo analogue. The ring centroid separation distances are about 3.2 Å and carbon–carbon contacts between the contiguous rings are 0.3 Å shorter than the sum of van der Waals radii. The spin-coupling of the two unpaired electrons between the two anion radical rings (forming a stacked dimer) correlates with the diamagnetic property of the crystals. Magnetic properties of alkali salts of tetrahaolgenosemiquinone anion radical acetone solvates were examined by electron paramagnetic resonance spectroscopy.