Li2MoO4 modified Li4Ti5O12/C anode material has been synthesized by a ball-milling assisted rheological phase reaction method. The structures, morphologies and electrochemical properties of the as-prepared materials have been analyzed by different physical and electrochemical methods. The results show that the amorphous carbon is successfully coated on the surface of Li4Ti5O12 nanoparticles with partial doping of Mo6+ into the Li4Ti5O12 structure. Electrochemical results indicate that Li2MoO4 modified Li4Ti5O12/C samples deliver improved rate capability and decreased charge transfer resistance. Among the investigated samples, the one with 5 wt% Li2MoO4 sample exhibits the optimal electrochemical properties and it shows a large capacity of 167.5mAhg−1 at 1C rate, which is close to its theoretical capacity. Even at 10C, its charge capacity is up to 137.5mAhg−1 with a high capacity retention of 92.5% after 200 cycles. The excellent electrochemical properties should be attributed to the improvement of electrochemical kinetics by the synergistic employment of reducing particle size, partial Mo6+ doping and Li2MoO4/C modification.