Porous titanium biomaterials manufactured using additive manufacturing techniques such as selective laser melting are considered promising materials for orthopedic applications where the biomaterial needs to mimic the properties of bone. Despite their appropriate mechanical properties and the ample pore space they provide for bone ingrowth and osseointegration, porous titanium structures have an intrinsically bioinert surface and need to be subjected to surface bio-functionalizing procedures to enhance their in vivo performance. In this study, we used a specific anodizing process to build a hierarchical oxide layer on the surface of porous titanium structures made by selective laser melting of Ti6Al4V ELI powder. The hierarchical structure included both nanotopographical features (nanotubes) and micro-features (micropits). After anodizing, the biomaterial was heat treated in Argon at different temperatures ranging between 400 and 600 degrees C for either 1 or 2 h to improve its bioactivity. The effects of applied heat treatment on the crystal structure of TiO2 nanotubes and the nanotopographical features of the surface were studied using scanning electron microscopy and X-ray diffraction. It was shown that the transition from the initial crystal structure, i.e. anatase, to rutile occurs between 500 and 600 degrees C and that after 2 h of heat treatment at 600 degrees C the crystal structure is predominantly rutile. The nanotopographical features of the surface were found to be largely unchanged for heat treatments carried out at 500 degrees C or below, whereas they were partially or largely disrupted after heat treatment at 600 degrees C. The possible implications of these findings for the bioactivity of porous titanium structures are discussed. (C) 2013 Elsevier B. V. All rights reserved.