SummaryTo combat the serious agglomeration and growth of the active materials, huge volume expansion and sluggish kinetics of metal oxides in the process of Li+ insertion/extraction, constructing hybrid nanostructures aiming to anchor active materials has been pursued. However, it is still limited in terms of capacity decay and complex preparation process. Herein, the hybrid MoO2/C is synthesized through a novel molten‐salt‐assisted approach, in which isolated small MoO2 nanoparticles were anchored on the well‐developed coal‐based porous carbon framework. The novel MoO2/C electrodes demonstrate enhanced electrochemical performance as Li+ battery anodes with a higher capacity of 960 mAh g−1 at 200 mA g−1, which is attributed to the synergistic effect for the uniform dispersion of MoO2 nanoparticles and coal‐based porous carbon layer with abundant active contact sites, which is better by far than the currently reported MoO2‐based electrode. Meanwhile, the hybrid MoO2/C exhibited improved extrinsic capacitive characteristics. Therefore, the hybrid MoO2/C constructed by the simple low cost strategy can be a prospective Li‐ion battery anode.