Epitaxially grown hematite (alpha-Fe2O3) films were obtained on the R-, A- and C-planes of sapphire (alpha-Al2O3) substrates by a coating-pyrolysis process in air and in an argon atmosphere. The X-ray diffraction theta-2 theta scanning and pole-figure analysis showed that the films have grown epitaxially to the substrate surfaces after heat treatment at 500 degrees C and higher. The crystallinity of the films was evaluated in terms of a full width at half maximum (FWHM) of the alpha-Fe2O3 104 peak in the phi scans. The crystallinity of the films increased after annealing in air up to 1000 degrees C, while the highest epitaxy was obtained at 600 degrees C in argon. The degraded crystallinity of the films prepared in argon at higher temperatures is attributed to the reaction between the film and the substrate due to a decrease in local oxygen partial pressure caused by an organic residue in the prefired films.