Si nanocrystals embedded in SiO 2 doped with P and Au at concentrations in the range of 1×10 18–3×10 20 cm −3 exhibit photoluminescence quenching. Upon increasing the Au concentration, a gradual decrease in nanocrystal photoluminescence intensity is observed. Using a statistical model for luminescence quenching, we derive a typical radius of ∼3 nm for nanocrystals luminescing around 800 nm. Au doping also leads to a luminescence lifetime reduction, which is attributed to energy transfer between adjacent Si nanocrystals, possibly mediated by the presence of Au in the form of ions or nanocrystals. Doping with P at concentrations up to 3×10 19 cm −3 leads to a luminescence enhancement, most likely due to passivation of the nanocrystal–SiO 2 interfaces. Upon further P doping the nanocrystal luminescence gradually decreases, with little change in luminescence lifetime.