It has been experimentally shown that high-temperature (1000-1100 °C) annealing (HTA) of a-Si/ZrO[2] and a-SiO[x]/ZrO[2] multilayered nanoperiodic (5-11 nm) structures (MNSs) gives rise to observation of intensive room-temperature photoluminescence (PL) in the range of 750-850 nm. Raman scattering spectra of MNSs confirms formation of Si nanocrystals in silicon-contained layers of the structures by HTA, that are responsible for this PL band. The influence of small Si clusters, oxide defects and defects at heteroboundaries are discussed.