The effect of high temperature (500–1100 °C) annealing of alfa-SiO[x]/SiO[2] multilayered nanoperiodic structures (MNS) formed by evaporation from two independent sources have been investigated. With results of analyzing the structure by high-resolution transmission electron microscopy it was concluded that during annealing at 1000–1100 °C in alfa-SiO[x]-layers of MNS vertically ordered arrays of silicon nanocrystals with a diameter not exceeding the initial thickness of alfa-SiO[x]-layers, with surface density ~ 10{12} cm{-2} are formed. The resulting structure with arrays of silicon nanocrystals in SiO[2] characterized size-depended photoluminescence at room temperature in 700–850 nm- wavelength range.