This study explores the preparation and characterization of TiO2/SnO2, with a specific focus on influence of MgO doping on their structural and optical properties. TiO2/SnO2 and TiO2/SnO2/MgO thin films were prepared by using the E-beam evaporation method. The X-ray diffraction (XRD) analysis of TiO2/SnO2 confirmed the crystalline nature of the prepared thin films, revealing the presence of anatase TiO2 and rutile SnO2 phases. The structural integrity was found to be influenced by the doping of MgO, as evidenced by variations in peak intensities. MgO doping can lead to development of new phases. The XRD analysis of TiO2/SnO2/MgO reported the new phases, such as MgTiO₃, Mg2TiO4 and Mg2SnO4, which are formed due to the interactions between MgO, TiO2 and SnO2. The TiO2/SnO2/MgO exhibit higher optical absorbance compared to TiO2/SnO2 samples. The impact of the MgO layer on the films’ structural and optical characteristics is responsible for this variation in absorbance. The estimated band gaps were calculated using the tauc plots, revealing an increase in the bandgap from 4.10 eV to 4.32 eV after MgO doping. FTIR analysis provides valuable insights into structural and chemical properties of thin films. 2D and 3D AFM analysis highlights the significant role of MgO in tailoring surface morphology and topography of TiO2/SnO2 thin films and improving functional properties. These findings suggest that the prepared TiO2/SnO2/MgO thin films may use in many applications such as optoelectronics, catalysis and environmental remediation.