A novel perpendicular magnetic material was obtained in the annealed Co/native oxide/Pd multilayer films. Upon thermal annealing in a vacuum, a sharp transition of magnetic anisotropy from in-plane to out-of-plane is observed for the Co/native oxide/Pd multilayers with 20 Å Co layers. These annealed Co/native oxide/Pd multilayers possess extremely large effect perpendicular anisotropy field (Heff) and perpendicular anisotropy energy (Ku), with the maximum Heff of 17 kOe and Ku of 5.1×106 erg/cm3 obtained in the annealed Co(20 Å)/native oxide/Pd(10 Å) multilayers. Moreover, the large perpendicular magnetic anisotropy sustains with annealing temperature varying from 200°C to 400°C, indicative of high thermal stability. The present results open the way to a third alternative for the realization of thermally stable perpendicular magnetic electrodes of tunnel junctions.