Tm-doped Ga2O3 films hold significant promise for application in light-emitting diodes (LEDs). A comprehensive understanding of their photoluminescence properties is pivotal for unlocking their full potential. In this work, we present findings on the photoluminescence (PL) spectra of Tm-doped Ga2O3 films, elucidating variations at different measurement temperatures and excitation energies utilizing synchrotron radiation light. The intensity of ultraviolet light (UVL1 and UVL2) exhibits a temperature dependence and its activation energy illustrates an ionization energy of shallow donor and migration through tunneling of self-trapped holes to triply ionized Ga vacancy (VGa) centers forming doubly ionized VGa acceptors. Additionally, the excitation energy-dependent PL spectra provide insights into the excitation mechanism of Tm ions, indicating a most likely through defects in the Ga2O3 host.