A composite of MoO2–Mo2C–C is fabricated through a facile ion-exchange route for the first time as an alternative anode material for lithium-ion batteries (LIBs). A macroporous cinnamic anion-exchange resin interacts with ammonium molybdate tetrahydrate in aqueous solution, and the product is then calcined under an inert gas atmosphere. The interaction between the resin and ammonium molybdate tetrahydrate results in an atomic level dispersion of the molybdenum over the organic carbon precursor (resin), while the calcination process allows the formation of MoO2 and Mo2C as well as the pyrolysis of resin to solid carbon. According to field-emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements, ultrafine MoO2 and Mo2C nanoparticles are uniformly dispersed but firmly attached within an amorphous carbon framework. When evaluated as an anode material, the as-synthesized sample exhibits superior electrochemical performance. The specific discharge capacity is as high as 1491 mA h g−1 in the first cycle and 724 mA h g−1 over 50 cycles at a current density of 0.2 A g−1. This simple, environmentally friendly, low-cost and easily scaled up method, has significant potential for mass industrial production of MoO2-based material as next-generation anode material of LIBs with wide application capability.