In order to have optoelectronic function integrated in a single chip, it is very important to obtain a silicon compatible material with an optimal Photoluminescence (PL) response. The Silicon Rich Oxide (SRO) has shown intense PL and is also compatible with silicon technology. In this work, the composition and optical properties of the SRO films are studied using null Ellipsometry, Fourier Transformed Infrared spectroscopy (FTIR), and Photoluminescence (PL). The SRO films were annealed at high temperature during different times. The IR absorption spectra show the presence of three characteristics Si-O-Si vibrations modes in SiO2. However, changes in their intensity and position were observed when annealing time and silicon excess were varied. These changes are directly related with structural variation in the SRO films. PL spectra show a considerable emission in the range 650 to 850 nm that varies with different thermal treatment times.