The need to identify lithium ion battery anodes consisting of new materials that display high energy density and good cycling stability has interested the research on reversible so-called conversion reaction between lithium and molybdenum oxides such as ternary metal oxide (Li2Mo4O13). Polycrystalline Li2Mo4O13 was synthesized by conventional solid-state reaction route and explored as new potential anode material for secondary lithium ion battery applications vs. Li+/Li in half-cell mode. The electrochemical performance of the Li2Mo4O13 electrode was studied by cyclic voltammograms and galvanostatic discharge-charge cycling under different rates. In the working voltage between 2.5 V and 0.1 V, Li2Mo4O13 shows a high first charge capacity of 1062 mAh g−1 at current rate of C/10 (24 Li react with 10 h) and a superior rate capability with capacity retention of 1008, 842, 713 and 640 mAh g−1 under current rates of C/10, C/5, C/3 and C/2 (24Li react with in 2 h), respectively. Further, the cycling performance was evaluated at C/3 rate (424 mA g−1) and after 100 cycles a reversible capacity of 550 mAh g−1 was obtained with columbic efficiency of ∼100%. Ex-situ XRD studies confirmed that the electrochemical reaction involves insertion of 5Li/f.u vs. Li+/Li during discharge to 1.3 V and the crystal structure was retained when charged to 2.5 V. Below 0.8 V, conversion reaction occurs leading to amorphization of the phase. When discharged to 0.1 V, Mo+6 is reduced to Mo0 state on the basis of the conversion reaction.