The perpendicular magnetic anisotropy (PMA) arising at the interface between ferromagnetic transition metals and metallic oxides was investigated via first-principles calculations. In this work very large values of PMA, up to 3 erg/cm 2 , at Fe|MgO interfaces are reported, in agreement with recent experiments. The origin of PMA is attributed to overlap between O-p z and transition metal d z 2 orbitals hybridized with d xz(yz) orbitals with stronger spin-orbit coupling-induced splitting around the Fermi level for perpendicular magnetization orientation. Furthermore, it is shown that the PMA value weakens in the case of over-or underoxidation due to the fact that oxygen p z and transition metal d z 2 orbital overlap is strongly affected by disorder, in agreement with experimental observations in magnetic tunnel junctions.