The thermal decomposition of c-plane GaN/sapphire templates was studied in a metalorganic vapor phase epitaxy (MOVPE) system installed in a laboratory-level X-ray diffractometer by using in situ X-ray reflectivity (XRR). GaN remained thermally stable in pure N2 up to 900 °C, while a significant decomposition occurred at 950 °C. Then, thin In
x
Ga1-x
N epilayers were grown on the annealed templates at 830 °C. In situ XRR measurements were conducted before and after InGaN growth. By theoretical and experimental analyses of the XRR spectra, the sample structure change upon thermal annealing was clarified. Photoluminecescence (PL) and atomic force microscopy (AFM) results demonstrated that thermal annealing affected the optical properties and microstructures of InGaN films. The PL peaks from InGaN slightly blue-shifted with thermal annealing.