TiO2-based nanotubular surfaces have promising properties for various industrial applications, such as solar cells, fuel cells, photocatalysis, energy storage, gas sensors, and biomedical applications. However, they have very limited use in real applications, and one of the major limiting factors is the weak adhesion of nanotubular surfaces to the substrate. In this study, nanotubular surfaces are formed on Ti6Al4V alloy by anodic treatment followed by a heat treatment at 500 °C for 3 h under an open atmosphere. Microstructural investigations revealed self-organized nanotubes grown on both α and β phases. High-resolution TEM/STEM analysis showed crystallization of the nanotubular layer and formation of additional oxide interlayers resulting in a drastic improvement in tribocorrosion resistance. These findings indicated that a simple heat treatment can significantly alter the properties of nanotubular layers and can widen their usage mainly for load-bearing implant applications in corrosive environments.