Recently, titanium oxide has been widely investigated as a carrier-selective contact material for silicon solar cells. Herein, titanium oxide films were fabricated via simple deposition methods involving thermal evaporation and oxidation. This study focuses on characterizing an electron-selective passivated contact layer with this oxidized method. Subsequently, the SiO2/TiO2 stack was examined using high-resolution transmission electron microscopy. The phase and chemical composition of the titanium oxide films were analyzed using X-ray diffraction and X-ray photoelectron spectroscopy, respectively. The passivation quality of each layer was confirmed by measuring the carrier lifetime using quasi-steady-state photoconductance, providing an implied open circuit voltage of 644 mV. UV−vis spectroscopy and UV photoelectron spectroscopy analyses demonstrated the band alignment and carrier selectivity of the TiO2 layers. Band offsets of ~0.33 and ~2.6 eV relative to the conduction and valence bands, respectively, were confirmed for titanium oxide and the silicon interface.