The paper presents the study of the lateral photovoltaic effect in the SiO2/TeO2/Bi2Te3/n-Si(111) multilayer structure. The spectral dependences of photosensitivity identify the localization of the photogeneration process in the space charge region of the silicon substrate at the bismuth telluride layer thickness of 5 nm or more and in the Bi2Te3 layer at its thickness of less than 5 nm. It is established that lateral photosensitivity can serve as an indicator of the natural oxidation process of the protective transparent covering. We defined that the studied structure demonstrates promising results as photovoltaic cell when the Bi2Te3 layer thickness of 5 nm and illumination parameters of λ = 730−830 nm and W = 0.8 mW.