Fullerenes encapsulating metal atoms have many possible uses in technology and even in bio-medical applications.1 Some fullerenes have been found to have two incarcerated metal atoms such as M2@C80 (M = La; Ce; etc.).2 Here we report the structural and electronic properties of Ce2@C80 calculated using density functional theory. We have found that Ce2@C80 has a D3d symmetric ground state structure and that Ce binds to a different type of binding site compared to other cerium containing fullerenes; such as Ce@C823 and even in Ce@C80. Fig: This binding site also differs compared to La in La2@C80; which is D2h symmetric. Since each of the six-membered rings in Ih-C80 satisfies the proposed criteria for (M=La; Ce) binding3; we here analyze and discuss the reason of Ce binding to another site based on its frontier level orbitals in connection with the orbitals of La2@C80. We also discuss oxidation state of Ce in Ce2@C80; in comparison with the traditional Ce tri-halides compounds (CeCl3; CeF3) and the investigation on the simulated vibrational spectrum of the ground state isomer of Ce2@C80.