Photochemically generated benzyl radicals react with Sc3N@C-80-I-h to produce a dibenzyl adduct [Sc3N@C-80(CH2C6H5)(2)] in 82% yield and high regioselectivity. The adduct's H-1 spectrum revealed high symmetry: only one AB pattern was observed for the methylene protons. The C-13 NMR spectrum suggested a C-2-symmetrical structure. DFT calculations reveal that a 1,4-adduct is more favorable than a 1,2-adduct by > 10 kcal/mol. The 1,4-structure on [566] ring junctions was unambiguously confirmed by X-ray crystallographic analysis. UV-vis spectra revealed that the removal of two p orbitals from the pi system of the cage together with the benzylic substituents change the electronic properties of the metallofullerene in a manner similar to those reported for disilirane and trifluoromethyl moieties. Under the same conditions from LU3N@C-80-I-h we prepared (63% yield) Lu3N@C-80(CH2C6H6)(2), which demonstrated properties similar to the 1,4-dibenzyl adduct of SC3N@C-80-I-h.