We investigate the optical properties of high-quality Si nanocrystals (NCs)/SiO2 multilayers under high hydrostatic pressure with Raman scattering and photoluminescence (PL) measurements. The aim of our study is to shed light on the origin of the optical emission of the Si NCs/SiO2. The Si NCs were produced by chemical-vapor deposition of Si-rich oxynitride (SRON)/SiO2 multilayers with 5- and 4-nm SRON layer thicknesses on fused silica substrates and subsequent annealing at 1150 °C, which resulted in the precipitation of Si NCswith an average size of 4.1 and 3.3 nm, respectively. From the pressure dependence of the Raman spectra we extract a phonon pressure coefficient of 8.5 ± 0.3 cm−1/GPa in both samples, notably higher than that of bulk Si (5.1 cm−1/GPa). This result is ascribed to a strong pressure amplification effect due to the larger compressibility of the SiO2 matrix. In turn, the PL spectra exhibit two markedly different contributions: a higher-energy band that redshifts with pressure, and a lower-energy band which barely depends on pressure and which can be attributed to defect-related emission. The pressure coefficients of the higher-energy contribution are (−27 ± 6) and (−35 ± 8) meV/GPa for the Si NCs with a size of 4.1 and 3.3 nm, respectively. These values are sizably higher than those of bulk Si (−14 meV/GPa). When the pressure amplification effect observed by Raman scattering is incorporated into the analysis of the PL spectra, it can be concluded that the pressure behavior of the high-energy PL band is consistent with that of the indirect transition of Si and, therefore, with the quantum-confined model for the emission of the Si NCs.