We report on the composition and morphology of as-grown anodic oxide films onto the iron surface in an ethylene glycol solution containing some NH 4 F and H 2 O by anodizing under direct current bias. Decrease in the content of NH 4 F and the temperature of electrolyte allow us to form either nanochannel or nanotubular films over a larger potential window, ca. from 30 to 100V. By this way, the films in thickness of up to10μm have been formed. Mössbauer spectra recorded at room to cryogenic temperatures under conversion electron and transmission modes revealed the formation of lepidocrocite (γ-FeOOH) film containing some Fe(OH) 2 and/or FeF 2 ·4H 2 O. An increase in anodizing voltage results in fabrication of more porous and less Fe(II) compounds containing films.