In the crystal of the title substituted hemibiquinone derivative, C₁₆H₁₁BrN₂O₄or [BrHBQH₂(CN)₂], the substituted benzene rings are rotated about the central C—C bond, forming a dihedral angle of 53.59 (7)°. The ring systems interact through an intramolecular O—H...O_methoxyhydrogen bond, which induces a geometry quite different from those in previously reported hemibiquinone structures. In the crystal, the molecules associate through an intermolecular O—H...N_nitrilehydrogen bond, forming chains which extend along [100] and are interlinked through very weak C—H...N hydrogen bonds, giving a overall two-dimensional structure lying parallel to (010).