Research on well adherent, thick and nanoporous oxide film formation onto the metal substrates underwent a major burst throughout the last decade. In the current study, thick bi-layered films produced onto a pure iron surface by anodizing way in dimethyl sulfoxide (DMSO) electrolyte containing silica hexafluoride acid have been investigated upon the annealing in air. Compositional, phase and structural transformations of the film material to hematite, alpha-Fe2O3, were studied using Mossbauer spectroscopy at room to cryogenic temperatures, thermogravimetry (TG), differential thermal analysis (DTA), photoemission spectroscopy, scanning electron microscopy (SEM), and wave dispersive X-ray spectroscopy (WDX). Experimental findings indicated that much longer heating in air is required for these films to be fully transformed to hematite. This effect is linked here with the complex nature of DMSO films. Based on the combined WDX, photoemission and Mossbauer spectroscopy results, the transformations taken place during calcination of such amorphous films by heat-treatment in air to crystalline hematite have been determined. Investigations on the calcination effects of thick iron anodic films reported here offer opportunities for both fundamental research and practical applications. (C) 2011 Elsevier B. V. All rights reserved.