The effects of post-deposition annealing temperatures (400, 600, 800, and 1,000°C) in forming gas (95% N2 + 5% H2) ambient on metal–organic decomposed cerium oxide (CeO2) thin films deposited on n-type GaN substrate had been investigated. The occurrence of CeO2 phase transformation was reported and presence of CeO2, α-Ce2O3, and β-Ga2O3 had been detected, depending on the annealing temperature. As the annealing temperature increased, grain size and microstrains of CeO2 films were, respectively, increased and reduced. Metal–oxide–semiconductor characteristics of the annealed samples were systematically investigated. The highest dielectric breakdown field was perceived by sample annealed at 400°C due to the reduction of semiconductor–oxide interface trap density and effective oxide charge.