In this study, a novel nanocomposite material consisting of Bi2O3 and Bi2MoO6, named as Bi2O3@Bi2MoO6, was successfully fabricated by co-precipitation method in ethylene glycol solvent. Morphological analysis of the heat-treated sample at 400 °C for 12 h in Ar atmosphere (Bi2O3@Bi2MoO6 _400 °C) showed that it contained nano-sized particles of Bi2O3 and Bi2MoO6; in addition, an amorphous phase along with a crystalline structure was also observed. When used as an anode for Li-ion batteries (LIBs), Bi2O3@Bi2MoO6 _400 °C anode exhibits excellent electrochemical properties such as high Coulombic efficiency, high specific capacity, excellent capacity retention, and outstanding rate capacity. Specifically, the Bi2O3@Bi2MoO6 _400 °C anode presented a reversible capacity of 786 mAh g−1 at the beginning cycle at 0.1 A g−1 and retained about 90 % of the charging capacity value after 80 cycles. The advanced electrochemical properties of the nanocomposite anode are related to the combination of many aspects such as nanostructure, existence of amorphous phase, and pseudo-behaviour of metal-based components. The structural stability and electrochemical performance of the anode material, therefore, are improved. These results demonstrate Bi2O3@Bi2MoO6 _400 °C as a promising material for establishing high-performance LIB anodes.