The present study investigates the effect of fluorine species during anodizing of aluminium and AA2024-T3 alloy in sulphuric acid and tartaric-sulphuric acid (TSA) electrolytes. The investigation comprises four main parts; (i) Effects of fluoride on barrier film formation on aluminium. (ii) Effects of fluoride and fluorozirconic acid (FZ) on porous film growth on aluminium in sulphuric acid. (iii) Effects of FZ on porous film growth on aluminium and AA 2024-T3 alloy in sulphuric acid and TSA. (iv) Effects on anodizing of other fluoroacids (fluoroboric (FB), fluorosilicic (FS) and fluorotitanic acid (FT)). The anodic films were examined by analytical scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, Rutherford backscattering spectroscopy, nuclear reaction analysis and glow discharge optical emission spectroscopy. The behaviour of fluoride ions during the growth of barrier-type films on aluminium was investigated in ammonium pentaborate solution with added sodium fluoride. Additions of up to 3.5 x 10-3 M sodium fluoride had a negligible influence on the film growth. In contrast, 3.5 x 10-2 M sodium fluoride reduced the efficiency to 60% as fluoride ions promoted field-assisted ejection of Al3+ ions from the film. Incorporated fluoride ions migrated inwards at a rate about twice that of O2- ions, forming a fluoride-rich layer at the film base. The study of the influence of FZ on formation of porous anodic films in sulphuric acid and TSA employed a range of anodizing voltages, electrolyte temperatures and anodizing times. Fluoroacid increased the growth rate, with a reducing influence as the temperature increased. The films contained fluoride and sulphate ions, zirconium was not detected. The fluoride concentration decreased with increasing temperature, whereas the sulphate concentration was unaffected. Anodizing aluminium and AA 2024-T3 alloy in other fluoroacids resulted in similar influences on the anodizing behaviour as FZ. The differences in growth rate, film composition and film morphology were comparatively small and did not show a systematic dependence on the type of fluoroacid employed. Boron, silicon and titanium were not detected in the films.