This project was focused on the generation of porous and nanotubular anodic films on titanium and Ti-6wt.%Al alloy, and investigation of the key factors responsible for a transition between porous and nanotubular morphologies. Advanced analytical techniques were employed for characterisation of the anodic films, in particular scanning and transmission electron microscopies, including analytical transmission electron microscopy, Raman spectroscopy, nuclear reaction analysis, Rutherford backscattering spectroscopy and atomic force microscopy. Preparation of electron transparent sections for analysis by analytical transmission electron microscopy was undertaken using the focused ion beam technique. Initially, the influence of a post-anodizing rinsing treatment, using various media, on the morphology, structure and composition of anodic films generated on titanium in 0.2 M ammonium fluoride in glycerol, containing 0 and 5 vol.% added water, was investigated. Porous anodic films were formed in an electrolyte without added water followed by rinsing with ethanol. It was revealed that the oxide-rich nanotubes are embedded in a fluoride-rich matrix, with fluoride-rich material being more extensive and oxide-rich nanotubes being thinner-walled for the anodic films generated in the electrolyte with no added water followed by rinsing with ethanol compared with those for the films formed with added water to the electrolyte and rinsed similarly. However, post-anodizing rinsing of the former films transforms the porous morphology of the films to a tubular one. The contents of titanium and fluorine were reduced in the case of anodic films with the nanotubular morphology. It was suggested that dissolution of the fluoride-rich matrix occurs during rinsing of the specimens with water, leading to the transition from porous to nanotubular morphologies and subsequent loss of titanium and fluorine. Further work was undertaken to study the effect of ageing in deionised water on the morphology, structure and composition of the anodic films. It was revealed that loss of titanium and fluorine is greater for the films generated in the electrolyte with no added water followed by rinsing with water and ethanol and ageing compared with that for the films formed in the electrolyte with 5 vol.% added water followed by rinsing with water and ethanol and ageing. Finally, the anodic films generated on the Ti-6wt.%Al alloy were investigated. Porous anodic films were formed in the electrolyte without added water followed by rinsing with ethanol whereas the films treated with water disclosed nanotubular morphology. Porous anodic films contained greater amount of fluorine than nanotubular ones. Compositional analysis revealed an increased amount of fluorine for the anodic films generated on the alloy compared with those for the films formed on titanium under all investigated conditions. The difference in film compositions may be related to the difference in composition of the substrates used for anodizing, in particular, to the presence of aluminium as alloying element in the Ti-6wt.%Al alloy.