A room-temperature photoluminescence (PL) study of amorphous Si/amorphous silicon oxynitride multilayer films prepared by plasma-enhanced chemical vapor deposition is reported. The PL peak position can be tuned from 800 nm to 660 nm by adjusting the oxygen/nitride ratio in the a-SiOxNy:H sublayer. The Fourier transform infrared (FTIR) absorption spectra indicate that the shift of the PL peak position is accompanied by an increase in the Si-O-Si absorption peak’s intensity, which induces the structural disorder at the interface, resulting in an increase in band gap energy. The effects of size on the photoluminescence spectrum have been studied. As a result, it has been observed that the addition of oxygen atoms introduces a large number of localized states at the interface, causing a blue shift in the emission peak position. With an increase in oxygen atoms, the localized states tend to saturate, and the quantum phenomenon caused by the a-Si sublayer becomes more pronounced. It is found that, as the thickness of the a-Si sublayer decreases, the increase in the [O/N] ratio is more likely to cause an increase in disordered states, leading to a decrease in luminescence intensity. For a-Si/a-SiOxNy:H samples with thinner a-Si sublayers, an appropriate value of [O/N] is required to achieve luminescence enhancement. When the value of [O/N] is one, the enhanced luminescence is obtained. It is also suggested that the PL originates from the radiative recombination in the localized states’ T3- level-related negatively charged silicon dangling bond in the band tail of the a-Si:H sublayer embedded in an a-Si/a-SiOxNy:H multilayer structure.