The 5 different configurations of fullerene-cerium-porphyrin complexes are optimized using the Perdew-Burke-Ernzerhof (PBE) density functional theory. Judged from the geometrical criteria, C₆₀ and cerium porphrin can form supramolecular guest-host complexes. Binding energies also confirmed this conclusion. The most likely effect of orientation is the 5:6 C—C bond of C₆₀. In an effort to comprehend the underlying basis of this interaction, a decomposition of the interaction energies is also carried out using the extended transition state method. The results indicate that the contribution of the electrostatic energies to the total attractive energy is about 60%, it shows that electrostatic interaction is one of the main factors for stabilizing complexes. Lastly, the electron flow for complexes is studied, the results show that the guest-host interactions are also associated with a charge transfer from the cerium porphyrin moiety to the fullerene guest.