The obtention of luminescent SiO_xC_y:H thin films deposited by the HW-CVD technique is reported here. We study the effect of different monomethyl-silane (MMS) flow rates on the films properties. An increase in the emission bandwidth and a red-shift was observed when the MMS flow increased. The luminescence was related to optical transitions in band tail states and with less contribution from quantum confinement effects. After, the films were annealed at 750 °C in nitrogen. The annealed film deposited at the highest MMS flow showed an emission spectrum like the as-deposited film, suggesting the same emission mechanisms. By contrast, the annealed film deposited at the lowest MMS flow showed two emission bands. These bands are due to the activation of radiative defects related to oxygen-deficient centers. MOS-like structures were fabricated as electroluminescent devices using the annealed films. Only the structure of the film with the highest carbon content showed light emission in a broad band in the visible spectrum region in forward bias, with a maximum centered close to 850 nm. The light emission mechanism was related to electron thermalization in the band tail states and a direct hole injection into deep states. The trap-assisted tunneling, Poole–Frenkel emissions and Fowler–Nordheim tunneling were proposed as the charge transport mechanism.