CuSbS2 particles could be rapidly prepared by the microwave-assisted liquid phase method. Polyethylene glycol (PEG) was used as the directing agent for morphology and structure of CuSbS2 particles. Microwave irradiation could induce Cu2+, adsorbed on PEG chain structure, to reduce as Cu+. In the further reaction, the rod-like structure of CuSbS2 was formed. The results showed that the CuSbS2 particles prepared by the PEG400 structure directing agent had a higher first discharge specific capacity (~1499.6 mAh g−1) and excellent electronic and ionic conductivity. This method provides a new idea for the morphology control of anode materials for high energy density lithium batteries.