We report the structural and optical properties of ten-period ZnO/Mg x Zn1–x O multiple quantum wells (MQWs) prepared on the most widely used semiconductor material, Si. The introduction of a nanometer thick high-k Y2O3 transition layer between Si (111) substrate and a ZnO buffer layer significantly improves the structural perfection of the MQWs grown on top of it. The high structural quality of the ZnO/Mg x Zn1–x O MQWs is evidenced by the appearance of pronounced high order satellite peaks in X-ray crystal truncation rods; high resolution cross-sectional transmission electron microscopy images also confirmed the regularly arranged well and barrier layers. When the well width is less than ∼2.7 nm, the quantum-confined Stark effect in MQWs can be negligible. Not only the increasing exciton-binding energy but also reducing exciton–phonon coupling determined in temperature-dependent photoluminescence spectra indicate quantum-size effect. Our results demonstrate that ZnO/Mg x Zn1–x O MQWs integrated on Si have great potential in UV optoelectronic device applications.