Si nanocrystals embedded in a SiO 2 matrix were studied with positron annihilation and photoluminescence spectroscopies. Analysis of the S- and W-parameters for the sample annealed at 800 °C reveals a positron trap at the interface between the amorphous nanodots and the surrounding matrix. Another trap state is observed in the 1150 °C heat treated samples where nanodots are in a crystalline form. Positrons are most likely trapped to defects related to dangling bonds at the surface of the nanocrystals. Passivation of the samples results on one hand in the decrease of the S-parameter implying a decrease in the open volume of the interface state and, on the other hand, in the strengthening of the positron annihilation signal from the interface. The intensity of the photoluminescence signal increases with the formation of the nanocrystals. Passivation of samples strengthens the photoluminescence signal, further indicating a successful deactivation of luminescence quenching at the nanocrystal surface. Strengthening of the positron annihilation signal and an increase in the photoluminescence intensity in passivated silicon nanocrystals suggests that the positron trap at the interface does not contribute to a significant extent to the exciton recombination in the nanocrystals.