A comparative study of compositional and optical properties of silicon-rich oxide (SRO) films deposited by low-pressure chemical vapor deposition (LPCVD) and plasma-enhanced chemical vapor deposition (PECVD) is presented. Infrared spectra revealed the presence of hydrogen bonded to silicon atoms in the SRO–PECVD films, whereas in SRO–LPCVD films the IR spectra looked like the stoichiometric thermal silicon oxide. Moreover, X-ray photoelectron spectroscopy (XPS) studies showed that the SRO–PECVD films contain a higher content of nitrogen than SRO–LPCVD films. In spite of differences, the SRO films obtained by both methods show a strong room-temperature photoluminescence (PL). However, the highest PL intensity was emitted by SRO films obtained by LPCVD.