We report on the perpendicular magnetic anisotropy (PMA) behavior of heavy metal (HM)/ Fe alloy/MgO thin film heterostructures after an ultrathin HfO 2 passivation layer is inserted between the Fe alloy and the MgO. This is accomplished by depositing one to two atomic layers of Hf onto the Fe alloy before the subsequent rf sputter deposition of the MgO layer. This Hf layer is fully oxidized during the subsequent deposition of the MgO layer, as confirmed by X-ray photoelectron spectroscopy measurements. As the result a strong interfacial perpendicular anisotropy energy density can be achieved without any post-fabrication annealing treatment, for example 1.7 erg/cm 2 for the Ta/Fe 60 Co 20 B 20 /HfO 2 /MgO heterostructure. Depending on the HM, further enhancements of the PMA can be realized by thermal annealing to at least o 400 C . We show that ultra-thin HfO 2 layers offer a range of options for enhancing the magnetic properties of magnetic heterostructures for spintronics applications.