Gallium oxide (Ga2O3) thin films were grown on c-, a-, m-, r-plane sapphire substrates using a mist chemical vapor deposition system. Various growth temperature range of 400~600℃ was applied for Ga2O3 thin film deposition. Then, several structural properties were characterized such as film thickness, crystal phase, lattice orientation, surface roughness, and optical bandgap. Under the certain growth temperature of 500℃, all grown Ga2O3 featured rhombohedral crystal structures and well-aligned preferred orientation to sapphire substrate. The films grown on c-and r-plane sapphire substrates, showed low surface roughness and large optical bandgap compared to those on a-and m-plane substrates. Therefore, various sapphire orientation can be potentially applicable for future Ga2O3-based electronics applications.