α-Cr2O3 is used as a buffer layer for the growth of α-Ga2O3 on sapphire for power devices. Presently, the growth of crystalline corundum-structured metal oxides, except for αCr2O3 are performed with metal acetylacetonates. In this paper, we report, for the first time, the development of a crystalline α-Cr2O3 on c-plane sapphire with chromium acetylacetonate as precursor over a wide temperature range varying from 400 oC to 550 oC. The temperature range not only ensures the compatibility of the process with α-Ga2O3 technology but also satisfies the requirement that the window is large enough to adequately optimize the quality of crystalline α-Cr2O3 thin film. XRD, SEM, AFM and XPS was performed to analyse the quality of the crystalline α-Cr2O3 layer. The best quality α-Cr2O3 is obtained at 500°C with the molarity of chromium acetylacetonate being 0.05, with a deposition rate of 35.37 nm/min and a crystallite size of 31.21 nm.