Abstract: There are many kinds of impurities (vanadium, aluminum, silicon, etc.) in Bayer circulating mother liquor which would affect gallium purity and electrolysis efficiency. Therefore, this paper proposed a method of enrichment of gallium from Bayer circulating mother liquor by adsorption and liquid-liquid extraction (TBP) and provide high quality electrolytic raw materials for electrolytic gallium. The results showed that amidoxime chelating resin had a good selective adsorption for gallium. When adsorption time was 60 min, adsorption temperature was 35 ℃ and adsorption resin dosage was 4 g, the adsorption rate of gallium reached 82%. Acid had a good effect for desorbing Ga from resin. Desorption rate of Ga reached 75% with 1.5 mol/L HCl at room temperature in 10 min, and the Si and V were basically not desorbed. The extraction results showed that the gallium was extracted by volume fraction of 20% TBP (kerosene as diluent) in 3 mol/L HCl system. The extraction of gallium could reach 99%, and the aluminum extraction rate was basically zero. And then Ga was back-extracted, and back-extraction rate reached 96.63% with 1~4 mol/L NaOH at room temperature. The concentration of Ga in sodium hydroxide reached 5 000 to 6 400 mg/L without Al, Si and V. Achievement of the enrichment and purification of gallium was obtained. High concentration gallium solution can be obtained by combining process of resin adsorption and extraction. Concentration of Ga was 10 times higher than the existing process, and the solution did not contain vanadium, aluminum and silicon. When obtaining the same mass of Ga(OH)₃, the acid and alkali dosage can be significantly reduced, and so do the agents cost.