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In view of the reported differences in biological bone tissue reactions to Ti and Ti6Al4V the aim of the work described herein was to establish whether direct‐current magnetron sputtered films would be realistic models of these materials which could then be used for in vitro studies of bone cell behavior. X‐ray photoelectron spectroscopy (XPS) was used to compare the surface chemistries of bulk‐passivated metals and the sputtered films. In the bulk passivated samples the predominant Ti oxide phase was 4+. However, Ti in its lower oxidation states was evident though closer to the bulk–oxide interface as seen by angle‐resolved XPS. The Al content of the passivated alloy oxide film was seen to be greatly enhanced (26 wt. %) over that of the stoichiometric alloy while V was reduced (1 wt. %). The surfaces of the sputtered films were very similar to their bulk passivated counterparts. Although there was indication that the distribution of the various Ti oxide phases within the film differed to that in the passivated oxide layer, it was concluded that the sputtered films may be developed as realistic substrata to model bone cell reactions to bulk passivated metals.