Li3P-VP nanocomposite has been formed by a homemade pulsed laser deposition route and its electrochemical characteristic with lithium is reported for the first time. It displays high lithium storage capability as electrode material for secondary lithium ion batteries. The Li3P-VP nanocomposite exhibits high specific discharge capacity of 1040.4mAhg−1 between 0.01 and 4.0V and the specific capacity can still maintain 95% after 50cycles. Ex situ transmission electron microscopy reveals that VP2 is generated from Li3P and VP after the first charging process to 4.0V, while Li3P and V are found to be the final discharge products. In the recharging process, VP and VP2 are formed as the delithiated products.