High quality CdZnTe films were prepared on GaN substrates by a close-spaced sublimation method and ZnTe transition layers were introduced to decrease the lattice mismatch between substrates and CdZnTe films for the first time. The morphology and structure of multilayer films were measured by x-ray diffraction and scanning electron microscopy. The crystalline quality of CdZnTe films based on ZnTe transition layers is obviously optimized and the best full width at half maximum and grain size of CdZnTe films are 0.149 • and 10.4 µm, respectively. A surface defect analysis of multilayer films was studied by x-ray photoelectron spectroscopy and low temperature photoluminescence, which indicated that the introduction of ZnTe transition layer can reduce the Cd vacancy ratio of CdZnTe films from 22.9% to 13.3%. It is also found that the electrical properties of GaN/ZnTe/CdZnTe multilayer films show a similar PN junction effect and the best photo-dark current ratio reaches 38.8. The responsivity of multilayer films under 254 nm light is about 69.1 times more than that to 400 nm, which improves the detection of CdZnTe films in the solar-blind region effectively.