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 -230 kcal/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 (AIM) theory and Electron Localization Function (ELF) 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.