The method of preparing a negative active material for a non-aqueous electrolyte rechargeable battery includes mixing a vanadium compound and a lithium compound and then subjecting the mixture to first firing to obtain Li1.0(VxMy)1.0O2 having a layered halite type structure (where 0.5≦x≦1.0, 0≦y≦0.5, x+y=1, and M is selected from the group consisting of group 2 to 15 elements of the periodic table and combinations thereof); and adding a lithium compound to the Li1.0(VxMy)1.0O2 and then subjecting the resultant to second firing. The negative active material for a non-aqueous electrolyte rechargeable battery prepared according to the preparing method has high crystallinity, excellent charge and discharge characteristics at a high rate, and excellent charge and discharge cycle characteristics.