Anodized TiO₂ nanotube arrays have important applications in the area of photocatalysis and biomedicine. In this study, with the aim of improving the photocatalytic and biomedical properties of TiO₂ nanotube arrays, we prepared both single and double layer walled TiO₂ nanotube arrays and subjected them to hydrothermal treatment in strontium acetate solution. It was found that fluoride doped SrTiO₃/TiO₂ nanotube arrays could be formed after hydrothermal treatment without the failure of the single and double layer walled structure. In the case of fluoride doped SrTiO₃/TiO₂ nanotube arrays with a double layer walled structure, doping of fluoride induced a visible light response, formation of SrTiO₃ benefited the separation of photogenerated electron–hole pairs, and the double layer walled structure led to an enlarged surface area. Due to the synergetic effect of above three factors, the fluoride doped double layer walled SrTiO₃/TiO₂ nanotube arrays demonstrated the highest photocatalytic activity under ultraviolet, visible and simulated solar light irradiation. The degradation rates of methylene blue solution are 0.13 h⁻¹, 0.26 h⁻¹ and 0.53 h⁻¹ respectively. Moreover, ability to induce hydroxylapatite formation on the surface was also examined through an immersing test in simulated body fluid. The results indicated that SrTiO₃, doped fluoride and a double layer walled structure could stimulate the hydroxylapatite formation by providing a larger number of hydroxyl ions, hydroxyl radicals and reactive initiation sites, thus the fluoride doped double layer walled SrTiO₃/TiO₂ nanotube arrays also exhibited the best ability to form hydroxylapatite on the surface.