Ultra thin heteroepitaxial PrO(2) films on Si(111) were annealed under UHV conditions and investigated by x-ray diffraction (XRD), x-ray reflectometry (XRR) and spot profile analysis low energy electron diffraction (SPALEED) with regard to structural stability and phase transitions due to the high oxygen mobility of the oxide. This gives information about the manageability of the material and its application as a model catalyst system in surface science. While the samples are stable in UHV at room temperature, annealing at 300 °C exhibits a terminated phase transition from PrO(2) and PrO(2-Δ) to cub-Pr(2)O(3) with an increase in the silicate at the interface and a decrease in the crystalline praseodymia layer mainly due to atomic diffusion of silicon into the oxide film. Strain effects during the phase transition also cause mosaic formation at the surface. Further annealing up to 600 °C shows only little change in the film structure. This will finally lead to a model of the film structure during the annealing process.