Here, we report the first experimental and computational study of the noncovalent binding energies and structures of ionized benzenes containing electron-withdrawing substituents solvated by one to four HCN molecules. Measured by ion mobility mass spectrometric equilibrium studies, the bond dissociation enthalpies of the first HCN molecule to the fluorobenzene (C6H5F center dot(+)), 1,4-difluorobenzene (C6H4F2 center dot(+)), and benzonitrile (C6H5CN center dot(+)) ions (11.2, 11.2, and 9.2 kcal/mol, respectively) are similar to those of HCN with the benzene (C6H6 center dot(+)) and phenyacetylene (C6H5CCH center dot(+)) radical cations (9.2 and 10.5 kcal/mol, respectively). DFT calculations at the B3LYP/6-311++G(d,p) level show that HCN can form in-plane hydrogen bonds to ring hydrogens, or bind electrostatically to positively charged carbon centers in the ring. The electron-withdrawing substituents increase the bond energy by increasing the partial positive charge on the ring hydrogens that form CH delta+---NCH bonds, and by creating a pi hole, as evidenced by positive charge centers on the fluorinated ring carbons for electrostatically bonded isomers. In the complexes of benzonitrile(center dot+), similar to benzene(center dot+), hydrogen bonded planar isomers have the lowest energy. In the complexes of (fluorinated benzene)(center dot+), the lowest energy isomers are electrostatically bonded where HCN is perpendicular to the ring and its dipole points to a positively charged ring carbon. However, in all cases the planar hydrogen-bonded and vertical electrostatic isomers have similar binding energies within 1 kcal/mol, although HCN interacts with different sites of the ionized benzenes in these isomers, suggesting that the observed cluster populations are mixtures of the planar and vertical isomers. Further HCN molecules can bind directly to unoccupied ring CH hydrogens or bind to the first-shell HCN molecules to form linear HCN---HCN--- hydrogen bonded chains. The binding energies decrease stepwise to about 6-7 kcal/mol by 4 HCN molecules, approaching the macroscopic enthalpy of vaporization of liquid HCN (6.0 kcal/mol).