Si/SiO2 multilayers (MLs) have been prepared under different deposition temperatures (TS) by ion beam sputtering. The annealing at 1200°C leads to the formation of Si nanocrystals in the Si layer of MLs. The high resolution transmission electron microscopy images clearly demonstrate the existence of Si nanocrystals, which exhibit photoluminescence (PL) in the visible range when TS is ≥ 300°C. This is attributed to well-separation of nanocrystals in the higher-TS samples, which is thought to be a major cause for reducing non-radiative recombination in the interface between Si nanocrystal and surface oxide. The visible PL spectra are enhanced in its intensity and are shifted to higher energy by increasing TS. These PL behaviours are consistent with the quantum confinement effect of Si nanocrystals.