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.