The binary skutterudite CoSb₃ is a narrow bandgap semiconductor thermoelectric (TE) material with a relatively flat band structure and excellent electrical performance. However, thermal conductivity is very high because of the covalent bond between Co and Sb, resulting in a very low ZT value. Therefore, researchers have been trying to reduce its thermal conductivity by the different optimization methods. In addition, the synergistic optimization of the electrical and thermal transport parameters is also a key to improve the ZT value of CoSb₃ material because the electrical and thermal transport parameters of TE materials are closely related to each other by the band structure and scattering mechanism. This review summarizes the main research progress in recent years to reduce the thermal conductivity of CoSb₃-based materials at atomic-molecular scale and nano-mesoscopic scale. We also provide a simple summary of achievements made in recent studies on the non-equilibrium preparation technologies of CoSb₃-based materials and synergistic optimization of the electrical and thermal transport parameters. In addition, the research progress of CoSb₃-based TE devices in recent years is also briefly discussed.