Lithium insertion behaviour of alpha-CuVO3 was investigated. By chemical Lithium insertion using BuLi/hexane solution LixCuVO3 (x<0.25) was formed, and Cu(II) and V(V) in the oxide were reduced simultaneously. Insertion Limit was controlled by low diffusivity of lithium insertion product. Further lithium insertion occurred electrochemically, forming metallic copper, and this process seemed to occur reversibly to some extent.