The composition and morphology of the n-Al2O3 transition oxide layer at the Al-CdTe interface and the n-MoO3 oxide layer at the CdTe–Mo interface were studied in this work. The Schottky barrier was formed by depositing a polycrystalline p-CdTe layer by a gas-transport reaction in a hydrogen flow onto a Mo substrate. The Schottky barrier was obtained by vacuum deposition of an Al metal layer on the p-CdTe surface. X-ray diffraction phase analysis of the Al–p-CdTe–Mo structure made it possible to establish the real structure, which has the real structure of Al– Al2O3–p-CdTe–MoO3. Based on a scanning electron microscope (SEM), the composition of the Al-p-CdTe structure was studied, where Al is 1.7% Wt, Te is 52.3% Wt, and Cd is 46.0% Wt. The current-voltage characteristics of the Al-CdTe-Mo Schottky barrier in the forward and reverse directions have been studied. The influence of the MoO3 compound layer, which is a wide-gap semiconductor with an n-type orthorhombic structure with a band gap Eg = 2.68 eV, has been revealed. Based on the current-voltage characteristics of the structure, the n-MoO3 layer is determined by smoothing the barrier between the metal and the semiconductor, which affects the mechanism of charge transfer in the structure. The MoO3 compound is a source of electron injection, which is formed during the growth of p-CdTe between the layers of the Mo substrate and the CdTe polycrystalline film. For all samples in the spectral range 190÷900 nm, the absorption edge of Al2O3 films is not observed, which indicates a larger band gap of the oxide Eg ≥ 6.5 eV.