Abstract: The activation properties of ammonium oxalate on the flotation of pyrite and arsenopyrite in the lime system were studied in this work. Single mineral flotation tests showed that the ammonium oxalate strongly activated pyrite in high alkalinity and high Ca²⁺ system, whereas arsenopyrite was almost unaffected. In mineral mixtures tests, the recovery difference between pyrite and arsenopyrite after adding ammonium oxalate is more than 85%. After ammonium oxalate and ethyl xanthate treatment, the hydrophobicity of pyrite increased significantly, and the contact angle increased from 66.62° to 75.15° and then to 81.21°. After ammonium oxalate treatment, the amount of ethyl xanthate adsorption on the pyrite surface significantly increased and was much greater than that on the arsenopyrite surface. Zeta potential measurements showed that after activation by ammonium oxalate, there was a shift in the zeta potential of pyrite to more negative values by adding xanthate. X-ray photoelectron spectroscopy test showed that after ammonium oxalate treatment, the O 1s content on the surface of pyrite decreased from 44.03% to 26.18%, and the S 2p content increased from 14.01% to 27.26%, which confirmed that the ammonium oxalate-treated pyrite surface was more hydrophobic than the untreated surface. Therefore, ammonium oxalate may be used as a selective activator of pyrite in the lime system, which achieves an efficient flotation separation of S–As sulfide ores under high alkalinity and high Ca²⁺ concentration conditions.