Using variable-angle spectroscopic ellipsometry, we measure the pseudo-dielectric functions of as-deposited and annealed SiO2/SiOx multilayers (MLs). The SiO2(2nm)/SiOx(2nm) MLs have been prepared under various deposition temperature by ion beam sputtering. The annealing at temperatures ≥ 1100°C leads to the formation of Si nanocrystals (nc-Si) in the SiOx layer of MLs. Transmission electron microscopy images clearly demonstrate the existence of nc-Si. We assume a Tauc-Lorentzian lineshape for the dielectric function of nc-Si, and use an effective medium approximation for SiO2/nc-Si MLs as a mixture of nc-Si and SiO2. We successfully estimate the dielectric function of nc-Si and its volume fraction. We find that the volume fraction of nc-Si decreases after annealing, with increasing x in as-deposited SiOx layer. This result is compared to expected nc-Si volume fraction, which was estimated from stoichiometry of SiOx.