Although the advantages of transition metal oxides (TMOs) include low cost, convenient synthesis and high capacity, the severe volume expansion and modest conductivity restrain their extensive applications. In this work, we introduced carbon sources into MoO₂/Ni materials by high temperature annealing, and successfully obtained MoO₂/Ni/C composites with a three-dimensional (3D) flower-like structure. In addition, the outermost carbon coating can efficaciously boost the electrical conductivity of the MoO₂/Ni/C and buffer its volumetric expansion. As expected, the MoO₂/Ni/C sample shows a high lithium storage capacity of 808 mA h g⁻¹ after 200 cycles at 200 mA g⁻¹ when utilized as a lithium-ion battery (LIB) anode. Therefore, it also provides guidance for the construction and optimization of carbon-coated TMO anode materials for LIBs.