Abstract: The chlorination leaching with calcium salt system was used to recover the bismuth from the acid leaching residue of copper converter flue dust in the test.The influence factors including leaching test,neutralization test and nitric acid dissolution-iron powder replacement test were optimized.The influence of recycled solution on bismuth leaching was investigated.The results show that the bismuth leaching rate 93.6 % could be obtained when the liquid-solid ratio was 4∶1,the concentrated sulfuric acid addition was 30 g/L,the calcium chloride addition was 80 g/L,the leaching temperature was 65 ℃,the leaching reaction time was 2 h.The neutralization test used calcium carbonate to adjust the leaching solution pH to 3.0,bismuth oxychloride with bismuth mass fraction over 50 % was obtained.The precipitation rates of Pb, Sb and Bi were over 99 %, and the precipitation rates of Ag, As and Ca were 90 %, 60 % and 18 % respectively.Sponge bismuth with grade over 92 % after bismuth oxychloride was dissolved by nitric acid and replaced by iron powder.Good index can be achieved using recycled solution.Chlorination with calcium salt system realizes cyclic utilization of solution with high-concentration chlorine ions,lowers operation cost of enterprises and provids reference for wet recovery of the bismuth in the copper converter flue dust for smelting enterprises.