Cadmium telluride (CdTe) and zinc telluride (ZnTe), direct gap semiconductors with room‐temperature band gap energies of 1.45 and 2.25 eV, respectively, form a continuous series of solid solutions (Cd1−xZnxTe). The band gap energy of Cd1−xZnxTe can be tailored in the 1.45–2.25 eV range. Cd1−xZnxTe with band gap energy of 1.65–1.75 eV is suitable as the upper member of a two‐cell tandem structure for the photovoltaic conversion of solar energy. In this work, polycrystalline films of Cd1−xZnxTe have been deposited on glass, CdS/SnO2:F/glass, and Cd1−xZnxS/SnO2:F/glass substrates at 400 °C by the reaction of dimethylcadmium (DMCd), diethlyzinc (DEZn), and diisopropyltellurium (DIPTe) in a hydrogen atmosphere. The composition of Cd1−xZnxTe films determined by wavelength dispersive spectroscopy and x‐ray diffraction has been correlated with the band gap energy deduced from the junction photovoltage spectroscopy and optical transmission. The structural and electrical properties of Cd0.7Zn0.3Te (band gap energy 1.70 eV) films have been evaluated. Thin film Cd0.7Zn0.3Te/CdS and Cd0.7Zn0.3Te/Cd0.7Zn0.3S heterojunctions have been prepared and characterized.