Using a coating-pyrolysis process, an alpha -Fe2O3 film, which consists of densely packed epitaxial alpha -Fe2O3 particles with a rectangular shape, was obtained when an iron 2-ethylhexanoate solution was spin-coated onto an alpha -Al2O3 (012) substrate rinsed with methanol, and subsequently annealed in air. When the alpha -Al2O3 substrate was rinsed with other conventional solvents, such as toluene, etc., round-shaped particles were formed on the substrate. Since densely packed rectangular crystals of alpha -Fe2O3 were formed only on the substrate rinsed with methanol, methanol molecules adsorbed on the alpha -Al2O3 substrate are considered to promote alpha -Fe2O3 to form a densely packed layer of rectangular crystals. The ordered adsorption of iron 2-ethylhexanoate molecules through methanol molecules is discussed.