Theoretical investigation of different benzene–transition metal cation (V + (1); Cr ++ (2); Mn + (3); Fe ++ (4); Co + (5); Ni ++ (6); Cu + (7)) complexes has been performed at the B3LYP/6-311+G ∗ level. All the complexes show large interaction energy (−50 to −230kcal/mol). Complexes 3, 4 and 7 showed no benzene ring deformation. However, complexes 1, 2, 5 and 6 revealed a boat-like benzene disposition. The electronic properties of the complexes were analyzed by means of the atoms-in-molecules theory and electron localization function topological analysis. From the above analysis, 1 and 5 showed large benzene ring bond differentiation, and medium to low interaction energy, and consequently presented good properties as catalysts in dehydropolycondensation processes of polyaromatic hydrocarbons.