Ⅰ2-Ⅱ-Ⅳ-Ⅵ4 type semiconductor copper-zinc-tin-sulfur (CZTS) has outstanding advantages in terms of cost, constituent element abundance, toxicity and stability, and is considered as a promising solar energy harvesting material for green and cost-effective photovoltaic applications. Cu2ZnSn(S,Se)4 possesses chalcopyrite-like crystal structure and photoelectric performance. Nevertheless, the champion efficiency is still far behind its counterpart Cu(In,Ga)Se2(23.5%). The current research in this field focus on the optoelectronic properties of polycrystalline thin film materials and devices, leads to unclear identification of defect states and regulation of energy bands, which has become a bottleneck for breakthroughs in the performance of CZTS-based optoelectronic devices. This article reviews the research progress of CZTS-based single crystal materials, introduces its crystal structure and physical properties in detail, and summarizes the preparation technology of high-quality single crystal by travelling heater method, iodine transport method and flux method. The research on multi-type nanocrystal library and the physical properties of natural kesterite are also introduced. The optical and electrical properties of the prepared CZTS-based single crystal materials are discussed. Finally, the article summarizes the application of CZTS-based single crystal materials in semiconductor devices, points out the existing problems, and provides possible development directions for improving the performance of Ⅰ2-Ⅱ-Ⅳ-Ⅵ4 semiconductor material devices.