Bonding of benzene molecules on the surface of neutral and charged Fe-7 clusters, which have pentagonal bipyramids (PBP), was studied by means of all-electrons density functional calculations. Dispersion corrections were done with the BPW91-D2 method using the 6-311++G(2d,2p) basis sets. With two less coordinated equatorial sites (bonded to four iron atoms) and one axial site (bonded to five atoms), a triangular face of Fe-7 emerges as the basic unit for the absorption of benzene moieties. Bonding of benzene (Bz) on such triangle yields the ground state (GS) for Fe(7)Bz, Fe(7)Bz(-), and Fe(7)Bz(+). Without dispersion, in the GS of Fe(7)Bz(-), the ligand is eta(6) coordinated with a single equatorial iron site, and in the GSs of Fe(7)Bz(2) and Fe(7)Bz(2)(-), each benzene moiety is eta(6) bonded on opposite equatorial sites. However, BPW91-D2 yields GS structures for Fe(7)Bz(2), Fe(7)Bz(2)(-), and Fe(7)Bz(2)(+), where the absorption is done on opposite triangles. Therefore, dispersion corrections are crucial for a proper study of Fe(7)Bz(2). The multiplicities (M = 2S + 1, where S is the total spin) of these species, 17, 16, and 18, respectively, are smaller than those of Fe-7(23), Fe-7(-)(22) and Fe-7(+)(24) showing important quenching of the magnetic moment of Fe-7. Bond dissociation energies (BDE), in kcal/mol, for Fe(7)Bz (32.7), Fe(7)Bz(+) (47.3), and Fe(7)Bz(-) (27.2) show bigger (smaller) values for the cation (anion). A similar picture was found for the BDEs of Fe(7)Bz(2). Ionization energies, 5.37 and 4.94 eV, for m = 1 and 2 are smaller than that of Fe-7, 6.00 eV; which is due to delocalization of the electrons through the network of 3d-pi bonds. Electron affinities of Fe(7)Bz(1,2) are also smaller than that of Fe-7, being mainly due to the increased repulsion.