Abstract When zinc hydrometallurgy is used to treat zinc oxide dust (ZOD), the fluorine (F) and chlorine (Cl) in the dust interfere with zinc electrowinning. To investigate the effectiveness of F and Cl removal from ZOD by different alkaline washing methods. Under the condition that 16 g/L Na 2 CO 3 was mixed with 6 g/L NaOH in equal volume 1:1 and reacted with the dust under the optimum condition of the liquid-solid ratio of 5 mL/g for 2 h at 70 °C, final pH of 10, and stirring intensity of 400 rpm, the dechlorination of cloth bag zinc oxide dust (CBZOD) and boiler zinc oxide dust (BZOD) were 94.81 % and 90.63 %, respectively, and the defluorination were 84.81 % and 24.50 %, respectively. To further reveal the reasons for the difficult removal of F from ZOD, a step extraction method and physical phase analysis of residue were used, which resulted in more than 98 % removable fluoride in CBZOD and up to 56 % insoluble residue in BZOD. Therefore, it is obvious that the removal effect is better due to the presence of large amounts of removable fluoride and chloride in CBZOD; the F states and percentage of insoluble fluoride are main reasons affecting the removal of F.