It is of great significance to discover new negative electrode materials featuring a low operating voltage, high capacity and improved initial coulombic efficiency for lithium ion batteries. This is the first report on the use of orthorhombic Li3V(MoO4)3 as a promising anode material that exhibits natural advantages over reported traditional metal oxides. High-crystalline Li3V(MoO4)3 nanoparticles decorated with carbon are synthesized by a facile mechanochemical route followed by low-temperature (480°C) calcination. The lithium storage ability of the prepared Li3V(MoO4)3 anode is fully tapped at 3.0–0.01V vs. Li+/Li, displaying a lower voltage plateau than the conversion-type metal oxides. It delivers a high reversible specific capacity of 999 mAh g−1 at 50mAg−1 and a high coulombic efficiency of 82.6%. Moreover, it maintains a capacity retention of 92% after 75 cycles at 500mAg−1. The GITT-determined Li+ diffusion coefficient ranges from 10−10 to 10–13 cm2 s−1 along with the voltage. The lithium storage mechanism indicates that Li3V(MoO4)3 can be considered a pre-lithiated material. In-situ XRD testing during the first cycle reflects the conversion reaction of Li3V(MoO4)3. These insights will benefit the discovery of novel anode materials for lithium-ion batteries.