The benchmark study of DFT methods on the activation energies of phosphodiester C3'-O and C5'-O bond ruptures and glycosidic C1'-N bond ruptures induced by electron attachment was performed. While conventional pure and hybrid functionals provide a relatively reasonable description for the C1'-N bond rupture, they significantly underestimate the energy barriers of the C-O bond ruptures. This is because the transition states of the later reactions, which are characterized by an electron distribution delocalized from the nucleobase to sugar-phosphate backbone, suffer from a severe self-interaction error in common DFT methods. CAM-B3LYP, M06-2X, and omega B97XD are the top three methods that emerged from the benchmark study; the mean absolute errors relative to the CCSD(T) values are 1.7, 1.9, and 2.2 kcal/mol, respectively. The C-O bond cleavages of 3'- and 5'-dXMP(center dot-), where X represents four nucleobases, were then recalculated at the M06-2X/6-31++G**//M06-2X/6-31+G* level, and it turned out that the C-O bond cleavages do not proceed as easily as previously predicted by the B3LYP calculations. Our calculations revealed that the C-O bonds of purine nucleotides are more susceptible than pyrimidine nucleotides to the electron attachment. The energies of electron attachment to nucleotides were calculated and discussed as well.