Li1+x V3O8 is a very promising cathode material for lithium secondary batteries. A novel technique has been developed to prepare Li1+x V3O8. The V2O5 sol is prepared via a “quencher” method by NH4VO3 as the raw material. Then it is mixed with LiOH solution. The spherical precursor is obtained by a spray drying method. Spherical Li1+x V3O8 powders are synthesized by sintering the spherical precursor. DTA/TGA is employed to analyze the precursor. The influences of the preparing conditions including initial ratio of Li/V, sintering time and temperature on crystal structure and electrochemical performance have been investigated. As a result, the Li1+x V3O8 particles obtained by sintering at 350°C for 24h are fine, spherical, narrowly distributed, well crystallized and having excellent electrochemical properties.