We investigated the native point defects in CeO2 by the density functional (DFT) +U method, and using a non-linear core-corrected norm-conserving Ce pseudopotential. We find the neutral oxygen vacancy (VO 0) in CeO2 to have a very low formation energy of only 0.39eV in the Opoor limit. It is a deep donor with negative U behavior, only stable in its neutral and doubly positive states. The anion Frenkel defect is found to be the lowest energy disorder defect, with a formation energy of only 2.08eV per defect site. These low formation energies arise from the improved transferability of our Ce pseudopotential for its +3 and +4 valence states. The negative U behavior of VO leads to excellent photo-catalytic behavior, while the low formation energy of the anion Frenkel defect leads to a superior oxygen storage-and-release capability.