Because of high lithium storage capacity, high first coulombic efficiency and low cost, Li2MoO3 has become a very attractive anode material for lithium-ion batteries. However, its cycling stability and severe polarization need further improvement. Besides, its reaction mechanism is unclear. In this work, Li2MoO3 is synthesized through ball milling and thermal reduction, and its electrochemical performance and reaction mechanism are investigated as anodes for lithium-ion batteries. The synthesized Li2MoO3 shows excellent cycling stability with high capacity. At a current density of 100mAg−1, it presents a first discharge capacity of about 835mAhg−1 with an initial coulombic efficiency of 97.6%. After 150 cycles, a discharge capacity of 902mAhg−1 is preserved. At a current density of 1600mAg−1, the compound exhibits a stable discharge capacity of about 556mAhg−1. It is revealed that the synthesized Li2MoO3 follows mixed insertion/conversion reaction mechanism.