In this report, we present on a research result of the microstructural and optical properties of ZnO/CuO multilayered films. Three types of multilayer ZnO/CuO stacks were prepared by pulsed laser deposition (PLD) on amorphous SiO2/Si substrates, and then annealed at 500oC for 30 min to improve crystallinity. TEM and XRD analysis of the thin films revealed the formation of multiple crystallographic defects and modification of the dominant growth plane. Consequently, near-band-edge emission in ZnO can be controlled through the number of CuO layers. The detailed microstructure and electro optical properties of multilayered ZnO/CuO thin films will be discussed.