Magnetron-sputtered iron films were potentiodynamically anodized at two different sweep rates to 50V in an ethylene glycol electrolyte containing ammonium fluoride and water. At a high sweep rate of 1.0Vs−1, a barrier-type anodic film was formed even though the current efficiency was as low as ∼50%. In contrast, a nanoporous anodic film developed at a low sweep rate of 0.05Vs−1, and the film-formation efficiency reduced to 37%. The main part of the anodic films consists of iron (III) hydroxyfluoride with a thin inner layer composed of FeF3. The inner fluoride layer is formed owing to the faster inward migration of fluoride ions compared to that of the oxygen species. During immersion or re-anodizing of the iron specimen with an approximately 100-nm-thick, barrier-type anodic film at and below 15V, thinning of the anodic film proceeded uniformly and film dissolution was enhanced by applying an electric field. The impact of the electric field on film formation and dissolution is discussed.