Ferromagnetic/noble metal multilayer (ML) frames are expected to serve as reliable building blocks in a variety of perpendicular magnetic anisotropy (PMA) based spintronic devices. However, ultrathin ML matrices are highly susceptible to unintended reduction of electron spin polarization in the as-grown or annealed states and often require a large repeat number. Here, we introduce a simple approach to achieve thermally stable PMA in ultrathin [Co/Pd]3 MLs involving the incorporation of an ultrathin CoO capping layer. The thickness and oxygen content of the CoO layer are critical parameters to achieve enhanced PMA in ultrathin [Co/Pd]3/CoO MLs post-annealed up to 400 °C. An extensive analysis of structural features identified that robust PMA characteristics in [Co/Pd]3/CoO MLs are linked with thermally activated oxygen atom diffusion leading to structural reconfiguration upon annealing. The possible origin of the enhanced PMA in our [Co/Pd]3/CoO ML samples after high-temperature annealing is discussed, thereby enabling their use in future spintronic-related devices.