ZnO/Zn/Al2O3 sandwich structures are grown on glass substrates by magnetron sputtering. The effect of Al2O3 layers on optical properties of ZnO/Zn/Al2O3 sandwich structures is investigated. Results indicated that as the deposition time of Al2O3 increases, violet peak centered at 402nm gradually shifted to 412nm and the intensity firstly decreases and then increases. We discuss the intensity change and shift of violet peak relating to VZn defects and the band alignment of ZnO/Zn/Al2O3 sandwich structures, respectively. We proposed that ZnO/Zn/Al2O3 sandwich structures can be approximately regarded as a quasiquantum-well-like structure. So the electron tunneling from Zn to Al2O3 layer is suppressed and the photogenerated carriers can be confined in the Zn Fermi level. In order to further understand the effect of posttreatment on optical properties of samples, samples are annealed in vacuum at 350°C for 1h. PL emissions are weakened with the increase of Al2O3 deposition time. Interestingly, at a same deposition condition, PL emissions are still improved after posttreatment. Combined Al2O3 layer modulation with annealing treatment, steady PL properties can be effectively improved.