Luminescent silicon-rich dielectric materials have been under intensive research due to their potential applications in optoelectronic devices. Silicon-rich nitride (SRN) and silicon-rich oxide (SRO) ilms have been mostly studied because of their high luminescence and compatibility with the silicon-based technology. In this chapter, the luminescent characteristics of SRN and SRO ilms deposited by low-pressure chemical vapor deposition are reviewed and discussed. SRN and SRO ilms, which exhibit the strongest photoluminescence (PL), were chosen to analyze their electrical and electroluminescent (EL) properties, including SRN/SRO bilayers. Light emiting capacitors (LECs) were fabricated with the SRN, SRO, and SRN/SRO ilms as the dielectric layer. SRN-LECs emit broad EL spectra where the maximum emission peak blueshifts when the polarity is changed. On the other hand, SRO-LECs with low silicon content (~39 at.%) exhibit a resistive switching (RS) behavior from a high conduction state to a low conduction state, which produce a long spectrum blueshift (~227 nm) between the EL and PL emission. When the silicon content increases, red emission is observed at both EL and PL spectra. The RS behavior is also observed in all SRN/SRO-LECs enhancing an intense ultraviolet EL. The carrier transport in all LECs is analyzed to understand their EL mechanism.