Room temperature cathodoluminescence and photoluminescence were used to study silicon rich oxide (SRO) films with 5.5% silicon excess. Intense blue and red luminescence emissions were found. A SRO film was deposited by low-pressure chemical vapor deposition and was annealed at 1100 °C by 3 h in a nitrogen ambient. The emission from the SRO films was modeled as being due to donor-acceptor-pair decay. Calculations have been made to obtain the first estimates of the donor and acceptor energy distributions in SRO films.