Na2Mo2O7 was synthesized by sol-gel route and tested as anode material for Li-ion battery applications vs. Li+/Li in half-cell mode for the first time. The first cycle discharge and charge capacities are 1348mAhg−1 and 937mAhg−1 , respectively at 321mAg−1. The electrochemical reaction during first discharge involves insertion of Li into the crystal structure followed by conversion reaction with associated amorphization of the phase. The material shows excellent capacity retention and rate capability. Even after 50 cycles, a capacity of 470mAhg−1 was observed at a high current density of 800mAg−1. The nanocrystalline Na2Mo2O7 reported in this study exhibited highest capacity among the Mo based oxides.