Thin films of Ga2O3:Mn have been deposited on silicon (100) substrates without intentional heating by radio frequency (RF) planar magnetron sputtering from a Mn-doped Ga2O3 target in an oxygen-argon mixture atmosphere. Microstructure and properties of the deposited Ga2O3:Mn films were systematically investigated as a function of the post-deposition annealing temperature in the range between 500 °C and 1200 °C. X-ray diffraction (XRD) measurements showed that the as-deposited Ga2O3:Mn films were of an amorphous structure in nature. The Ga2O3:Mn films became crystalline by the post-deposition annealing above 800 °C and the crystallinity of the films was continuously improved up to the annealing temperature of 1200 °C. It was shown that the annealed Ga2O3:Mn films possessed a monoclinic β-Ga2O3 phase having a textured structure with (400) and (−401) crystallographic planes oriented preferentially parallel to the substrate surface. The lattice parameters of the monoclinic β-Ga2O3 phase in the 1200 °C annealed Ga2O3:Mn films were measured to be a = 12.152 A, b = 3.043 A, and c = 5.785 A.