Thinfilm heterostructure Ta/CoFeB/TaOx can exhibit chiral magnetic textures such as skyrmions as well as spin-orbit torque induced zero field magnetization switching, which offers great promise for next-generation information storage technologies. Here, we provide a strong correlation between the structural and magnetic properties in as-deposited and annealed Ta (1 nm)/ CoFeB (1.5 nm)/ TaOx (1 nm) trilayer and Ta (1 nm)/ CoFeB (1.5 nm)/ Ta (t)/ CoFeB (1.5 nm)/ TaOx (1 nm)] multilayered stack with t = 0.5, 1 nm. Interestingly, x-ray reflectivity results indicate improvement in the interface quality post annealing up to 300 °C. While the thinner Ta spacer layer (0.5 nm) in the stack causes the formation of smaller interface width, the thicker Ta spacer (1 nm) results in relatively larger interface width. Annealing results in the enhancement of saturation magnetization (Ms) and uniaxial magnetic anisotropy (UMA) and the extent of variation is mostly determined by thickness of the spacer Ta layer. Magneto-optical Kerr effect measurement suggests the existence of strong two-fold UMA in the film stack with Ta spacer layer 0.5 nm, however, its strength diminishes as the Ta spacer layer thickness is increased to 1.0 nm. Furthermore, the in-depth chemical/electronic investigations using x-ray photoelectron spectroscopy technique reveal the formation of additional chemical states such as TaB and TaOB at the interfaces. Remarkably, Boron diffusion and likely oxygen migration from the Fe-oxide/Co-oxide in CoFeB to neighboring Ta layers improves the metallic nature of Fe and Co due to annealing. Note that the thicker Ta spacer has a significant impact on the chemical transformation at the interface in comparison to that of thinner Ta spacer layer. Overall, in these Ta/CoFeB multilayered stacks, the thickness of the Ta spacer layer and annealing temperature play a crucial role in controlling interface quality that eventually governs the magnetic characteristics. These results provide new insight into the interfacial electronic structure modifications which are essential for controlling DMI and stabilization of skyrmions in Ta/CoFeB multilayers for future spintronic device applications.