It is now widely acknowledged that the stability, performance, and life of prostheses fabricated from metallic materials are directly related to the compositional details of the layers formed on the surfaces of these components at the time of implantation. The thrust of the present investigation is thus the use of angle‐resolved x‐ray photoelectron spectroscopy for the identification of the differences in composition and thickness between the layers formed on the surface of a Ti–6Al–4V alloy specimen following exposure for 1 h to either laboratory air or wet steam.