Thin films of hematite find extensive applications in photoelectrochemistry, photocatalysis, and gas sensors. c-axis oriented hematite films have been directly grown on c-plane sapphire substrate using chemical method via hydrolysis of ferric cations. X-ray diffraction (XRD) reveals that the crystalline phases of the films and corresponding sediment produced in the solution were α-Fe2O3 and pure β-FeOOH, demonstrating the promotion of nucleation of hematite on sapphire substrate as a result of lowered interface energy. Phi-scan results indicate that the hematite films are grown with (0001) planes parallel to c-plane of Al2O3. Scanning electron microscopic observation shows that the hematite films are composed of pyramid-shaped nanocrystals with smooth surface facets.