Composite and multilayered Si/SiO2 structures have been grown by means of reactive magnetron sputtering of a pure silica target. This method is based on the different nature of the plasma during deposition: the plasma consists of either pure argon or an argon/hydrogen mixture for the growth of silica or Si-rich films, respectively. Using this process, Si-rich single layers and Si/ SiO2 multilayer structures have been successfully elaborated and characterised by infrared absorption spectroscopy, optical transmission measurements and transmission electron microscopy (conventional and high resolution). The superlattices have shown a significant photoluminescence signal whose energy is governed by the Si sublayer thickness.