Anodic oxidation of niobium has been investigated in an electrolyte solution containing calcium phosphate and calcium acetate. The oxide layer morphology has been determined by combining 3D Atomic Force Microscopy images and cross-sectional Field Emission SEM measurements. The surface sensitivity of high-resolution X-ray Photoemission Spectroscopy has been exploited to evaluate the chemical composition of the outermost oxide surface, a key feature in view of implant development. Anodic Spark Deposition (ASD) results in the formation of micrometer-thick oxide layers showing a porous morphology suitable for osseointegration purposes. Increasing the maximum potential attained during oxidation leads to an increase of the oxide thickness and pore size accompanied by a noticeable surface enrichment with calcium and phosphorus. Remarkably, a maximal Ca/P ratio of 1.8 was achieved for anodization at 250 V, promising for osseointegration thanks to the similarity with hydroxyapatite stoichiometry. Parallel experiments performed on titanium under the same conditions indicated a maximal Ca/P ratio of 1.3 and pores of smaller dimensions. The comparative analysis suggests that niobium may represent a promising alternative to titanium to be explored for implant development.