We prepared epitaxially grown Cr 2 O 3 thin films on Al 2 O 3 (0001) substrate by using radio frequency magnetron sputtering at room temperature followed by a rapid-thermal annealing process. It is shown that the phase and the crystallinity of as-grown samples depend on the flow ratios of the working gas (Ar/O 2 ). X-ray diffraction (XRD) results show that oxygen-rich CrO 3 phase having preferred orientation is formed when sputter-grown at room temperature under the working gas (Ar/O 2 ) flow ratios of 9:1 and 7:3. XRD Φ-scanning results exhibit that annealing causes the oxygen-rich CrO 3 phase to transform into epitaxial Cr 2 O 3 phase, which is confirmed by X-ray photoemission spectroscopy. The samples grown at the gas flow ratio of 9:1 exhibit very smooth surfaces with root mean square roughness of 0.1–0.3nm.