Silicon oxycarbide ( SiCO ) thin films were prepared by the RF reactive sputtering technique on n-type silicon substrates with the target of sintered silicon carbide ( SiC ), and high purity oxygen was used as the reactant gas. The as-deposited films were annealed at temperatures of 600°C, 800°C, and 1000°C under nitrogen ambient, respectively. The films were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and photoluminescence (PL) spectrophotometer. The results show that annealing temperature plays an important role in the structure and photoluminescence of the films. The temperature 600°C is the most favorable annealing temperature for SiO 2 crystallization and the formation of 6H- SiC crystal phase in the SiCO films. The intense PL peaks located at 375 nm and 470 nm are observed at room temperature. The origin of the PL was discussed.