It is well known that Si ion implantation into SiO2 and subsequent high-temperature anneals induce the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of rapid thermal annealing to enhance the photoluminescence intensity have been investigated. Ion implantation was used to synthesize specimens of SiO2 containing excess Si with different concentrations. Si precipitation to form nanocrystals in implanted samples takes place with a conventional furnace anneal. The photoluminescence intensity and the peak energy of emission from Si nanocrystals depend on implanted ion dose. Moreover, the luminescence intensity is strongly enhanced with a rapid thermal annealing prior to a conventional furnace anneal. The luminescence intensity, however, decreases when rapid thermal annealing follows conventional furnace annealing. It is found that the order of heat treatment is an important factor in intensities of the luminescence and that the luminescence peak energy is found to be dependent, but only by a small factor, on the thermal history of specimens. Enhancement is found to be typical for low dose samples. Furthermore, the observation that the prolonged anneal induces saturation and a blue shift of the luminescence strongly indicates the emission is not simply due to electron–hole recombination inside the Si nanocrystals. Based on our experimental results, we discuss the mechanism for the enhancement of the photoluminescence, together with the mechanism of photoemission.