The objective of this work is to study for the first time the combination of electron beam (EB) surface structuring and plasma electrolytic oxidation (PEO) with the aim of providing a multiscale topography and bioactive surface to the Ti6Al4V alloy for biomedical applications. Ca and P-containing coatings were produced via 45 s PEO treatments over multi-scale EB surface topographies. The coatings morphology and composition were characterized by a means of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The effect on the previous EB topography was evaluated by means of a 3D optical profilometry and electrochemical response via potentiodynamic polarization tests. In general, the PEO process, morphology, composition and growth rate of the coatings were almost identical, irrespective of the topography treated. Minimal local differences were found in terms of morphology, and the growth rate were related to specific topographical features. Nevertheless, all the PEO-coated substrates presented essentially the same corrosion resistance. Electrochemical tests revealed a localized crevice corrosion susceptibility of all the bare EB topographies, which was successfully prevented after the PEO treatment.