Anomalous growth of silicon (Si) nanocrystals (NCs) was observed during Raman scattering measurements of nanosilica SiOx (x=0.9) powder with an average diameter of 40 nm. It was found that Si NCs were formed by exposure to the laser beam. This photo-assisted synthesis is similar to the thermal synthesis of Si NCs, which forms Si NCs by thermally decomposing SiOx into Si and SiO2. However, the photo-assisted synthesis is more effective in forming Si NCs than the thermal synthesis. Even one second after irradiation of the nanosilica SiOx powder with laser, Si NCs with an average size of 5 nm were formed. The Si NC size increases with increasing the laser power and exposure time. It is interesting to observe a self-limited size for higher laser power and prolonged exposure. The photo-assisted synthesis of Si NCs is proved to be a promising technique with a wide range of applications in nanotechnology.