To significantly improve the electrochemical performance of ReS2, fluffy carbon-coated ReS2 nanoflowers (named as ReS2/C nanoflowers) are prepared with assistance of the polyethyleneglycol (PEG) as carbon source and surfactant. The carbon-coating structure of ReS2/C nanoflowers derived from PEG can improve the conductivity of the composites and relief the volume expansion of ReS2 during the cycling process. Furthermore, the fluffy structure and small size of ReS2/C nanoflowers controlled by PEG are propitious to the transmission of Li ion. Thus, the obtained ReS2/C nanoflowers exhibited a superior electrochemical performance compared with the pure ReS2, which exhibit a discharge capacity of 501 mAh g(-1) at 0.5 C as anode materials for LIB after 100 cycles, with a high capacity retention of 98%. This preparation of ReS2/C nanoflowers can provide guidance for improving the electrochemical performances of ReS2 for Li storage.