Abstract Nowadays, study of silicon-based visible light-emitting devices has increased due to large-scale microelectronic integration. Since then different physical and chemical processes have been performed to convert bulk silicon (Si) into a light-emitting material. From discovery of Photoluminescence (PL) in porous Silicon by Canham, a new field of research was opened in optical properties of the Si nanocrystals (Si-NCs) embedded in a dielectric matrix, such as SRO (silicon-rich oxide) and SRN (silicon-rich nitride). In this respect, SRO films obtained by sputtering technique have proved to be an option for light-emitting capacitors (LECs). For the synthesis of SRO films, growth parameters should be considered; Si-excess, growth temperature and annealing temperature. Such parameters affect generation of radiative defects, distribution of Si-NCs and luminescent properties. In this chapter, we report synthesis, structural and luminescent properties of SRO monolayers and SRO/SiO2 multilayers (MLs) obtained by sputtering technique modifying Si-excess, thickness and thermal treatments.