Structural and optical properties of Al2O3/TiO2 nanolaminates fabricated by atomic layer deposition (ALD) were investigated. We performed Raman spectroscopy, transmission electron microscopy (TEM), X-Ray reflectivity (XRR), UV-Vis spectroscopy, and photoluminescence (PL) spectroscopy to characterize the Al2O3/TiO2 nanolaminates. The main structural and optical parameters of Al2O3/TiO2 nanolaminates were calculated. It was established that with decreasing of the layer thickness, the value of band gap energy increases due to the quantum size effect related to the reduction of the nanograins size. It was also shown that there is an interdiffusion layer at the Al2O3/TiO2 interface which plays a crucial role in explaining the optical properties of Al2O3/TiO2 nanolaminates. Correlation between structural and optical parameters was discussed.