We study the magnetic anisotropic properties of as-grown and annealed Pd/Co/Pd trilayer films based on their atomic and electronic structures using extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES) spectroscopy and magnetic circular dichroism (XMCD) measurements. The annealed film exhibits interesting perpendicular magnetic anisotropy (PMA) whereas the as-grown film exhibits in-plane anisotropy. Cross-sectional transmission electron microscopic analysis together with the Co K-edge EXAFS results confirm the formation of an ordered-alloy CoPd phase in the annealed film, whereas the as-grown film has an hcp Co-like phase. Co L 3,2 -edge XMCD measurements reveal an enhanced ratio of the Co 3d orbital to spin moments of the annealed film providing evidence of the observed PMA upon annealing. Strong perpendicular magnetic anisotropy (PMA) is observed in annealed Pd/Co/Pd trilayer film. The effect of temperature on alloy formation, the relationship among the atomic/electronic structures, magnetic moments and PMA has been studied.