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A new technology was developed to recover V_2O_5 from Bayer spent liquor by ion exchange. The experimental results show that in the conditions of 105°C and 0.20-0.25 mass ratios between CaO in lime and A1_2O_3 in spent liquor, the precipitation rate of vanadium in Bayer liquor is more than 85%. The vanadium-bearing precipitation is leached by NaHCO_3 solution. The leaching rate of vanadium can reach 85% in the conditions of 95℃, 40 g·L~(-1) of NaHCO_3 concentration, and ventilating of CO_2. The 201×7 type of resin has good adsorption effect on vanadium in the leaching solution. The adsorption rate is more than 94% with the flow rate of 0.09 mL·min~(-1)·g~(-1) of leaching solution and the temperature of 40-50℃. By using 3 mol·L~(-1) of NaOH to desorb the saturated resin after adsorption at 40-50℃, a solution with more than 5 g·L~(-1) of V_2O_5 can be obtained. After roasting ammonium metavanadate that precipitates from the desorption solution when NH_4Cl is added at the temperature of 500-550℃ for 2 h, V_2O_5 with more than 99% of purity is obtained.