This study investigates and compares plasma electrolytic oxidation (PEO) coatings produced on wrought Ti6Al4V alloy substrates with those resulting from electron beam powder bed fusion (PBF-EB). For a duration of 1000 s, a phosphate/silicate electrolyte with a current density of 50 A/cm2 was employed to fabricate the coatings. Surface and polished cross-sections of the coated specimens underwent SEM and X-ray diffraction (XRD) analyses. The obtained coatings exhibit differences of up to approximately 18% in thickness and formation, as well as in their anatase phase. The anatase phase is present at a level of 54.09% in the substrates processed by PBF-EB and 38.54% in wrought substrates. After 1000 s of PEO, the coatings formed on the wrought substrates exhibited higher porosity and larger pores (>1 μm) compared to those produced on the PBF-EB specimens. The PBF-EB coatings had lower porosity because they contained fewer pores larger than 1 μm. The findings imply that the unique microstructural arrangement of PBF-EB-produced additively made Ti6Al4V materials plays a significant impact in the development and morphological properties of PEO oxide coatings.