Ga2O3, with its large band gap, is a promising material suitable for utilization in solar-blind photodetection. Sapphire with a higher lattice match with Ga2O3 was used as the substrate for epitaxial growth of Ga2O3. Here, the epitaxial layers of Ga2O3 were deposited by MOCVD on patterned sapphire substrates. The structure of epitaxial Ga2O3 layers on patterned substrates has been identified by X-ray diffractometry. To investigate the influence of the patterned substrates on the formation of epitaxial layers, thin Ga2O3 layers were grown on a flat sapphire substrate under the same conditions. Both types of samples were β-phase. However, no improvement in the layers’ crystalline quality was discovered when utilizing patterned sapphire substrates. In addition, the performance of the obtained two types of Ga2O3 photodetectors was compared. The photoelectric properties, such as responsivity, response speed, and detection capability, were different in the case of flat samples.