Many rare earth elements have been encapsulated in fullerene cages and their possible applications include quantum bits in quantum computing; MRI agents in bio-medical sciences and as superconductors; which have made them interesting species both as a molecule and as a material.1 Among such available fullerenes; Ih-C80 has interesting chemistry as the unstable isomer gets stabilized by encapsulating two metal atoms such as M2@C80 (M=La; Ce etc.).3 Ce2@C80 is one such species and is reported to be extracted over a decade ago; but until now only a few studies exploring its nature have been reported.4;5 Top and Side view of Ce2@C80 Hence; we have applied density functional theory to expand the investigation of Ce2@C80 further to have a closer look at its structural and electronic properties. Our calculations reveal preferential binding sites of the two Ce inside the Ih-C80 cage; which differs from other cerium containing fullerenes such as Ce@C82.6 The reason for this will be discussed and compared with experiments and with the results available for La2@C80.