Luminescent amorphous silicon nitride-containing dense Si nanodots were prepared by using very-high-frequency plasma-enhanced chemical vapor deposition at 250 °C. The influence of thermal annealing on photoluminescence (PL) was studied. Compared with the pristine film, thermal annealing at 1000 °C gave rise to a significant enhancement by more than twofold in terms of PL intensity. The PL featured a nanosecond recombination dynamic. The PL peak position was independent of the excitation wavelength and measured temperatures. By combining the Raman spectra and infrared absorption spectra analyses, the enhanced PL was suggested to be from the increased density of radiative centers related to the Si dangling bonds (K0) and N₄⁺ or N₂⁰ as a result of bonding configuration reconstruction.