This paper presents research on separating Cl- from zinc-bearing waste lixivium by using trioctylamine as an extractant, 2-octanol as a solvent, and sulfonated kerosene as a diluent. The effects of trioctylamine concentration, organic/aqueous phase ratio, extracting stages, and waste lixivium pH were investigated, and the process of stripping was also discussed. The optimal conditions were achieved. The extraction efficiency, separation factor, and stripping efficiency were calculated with optimal values of 99.47%, 595, and 99.99%, respectively. Besides, the extractant regenerated after stripping was observed without the emulsifying phenomenon. The mechanism of extraction and stripping was also discussed.