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.