Two charge-transfer bicomponent 1:1 crystals of polycyclic aromatic hydrocarbons (anthracene and tetracene) with a new acceptor molecule (perfluoroanthraquinone) were grown by slow evaporation from solutions in toluene. In both crystals, π-πstacks of alternating donor and acceptor molecules are observed. In the tetracene-perfluoroanthraquinone complex, face-to-face stacking is the prevailing intermolecular interaction, while in the complex of anthracene-perfluoroanthraquinone multiple interactions (stacking, F···H, O···H, F···F) of similar energy are observed, as revealed by the Quantum Theory of Atoms in Molecules method, resulting in the formation of polymorphic modifications, as determined by X-ray single crystal diffraction and differential scanning calorimetry. The charge-transfer degree was estimated to be equal to 0.04 and 0.08 e in anthracene- and tetracene-containing complexes, respectively.