The thermal stability of different lead oxide films prepared by reactive dc magnetron sputtering from a Pb target has been investigated. The temperature dependence of composition as well as structural and optical properties have been studied by Rutherford backscattering spectroscopy (RBS), X‐ray diffraction (XRD) and variable‐angle spectroscopic ellipsometry (VASE). Both XRD and RBS experiments confirm that different kinds of lead oxides are formed upon increasing the oxygen flow. Upon annealing at 500 °C, all samples form orthorhombic PbO. VASE studies show that the refractive index n and the band gap energy Eg increase with increasing annealing temperature. For films annealed at 500 °C, n is approximately 2.7 at 650 nm and a band gap energy of 2.8 eV is obtained, which corresponds to the value for bulk PbO. The stoichiometric changes observed by XRD on increasing the annealing temperature are discussed and supported by thermodynamics arguments.