The separation techniques of vanadium and molybdenum were summarized, and a new method of removal V(Ⅴ) from Mo(Ⅵ) by adsorption with chelate resin was presented. Nine kinds of chelate resins were used to investigate the adsorbent capability of V(Ⅴ) in ammonium molybdate solution with static method. The test results show that DDAS, CUW and CW-2 resins can easily adsorb V(Ⅴ) in ammonium molybdate solution, but hardly adsorb Mo(Ⅵ). The dynamic experimental results show more than 99.5% of V(Ⅴ) can be adsorbed, and the adsorption rate of Mo(Ⅵ) is less than 0.27% at 294-296 K for 60 min at pH 7.42-8.02. The mass ratio of V to Mo decreases to l/5 0000 in the effluent from 1/255 in the initial solution. The loaded resin can be desorbed by 5% NH3·H2O solution, and the vanadium desorption rate can reach 99.6%. The max concentration of vanadium in desorbed solution can reach 20 g/L, while the concentration of molybdenum is less than 0.8 g/L.