Recovery of bismuth and arsenic from copper smelter flue dusts after copper and zinc extraction was carried out by a hydrometallurgical process. The dusts were leached with a H2SO4-NaCl solution and precipitating bismuth and arsenic in the liquor was performed. The precipitate was leached with a 2 M sodium hydroxide solution and the obtained residue and liquor were used for preparation of sponge bismuth and sodium arsenic, respectively. The process parameters were preliminarily optimized and under the optimal conditions, the total recoveries of bismuth and arsenic are 90% and 42%, respectively. The purity of obtained sponge bismuth can reach up to above 90% under the optimal conditions. (C) 2012 Elsevier Ltd. All rights reserved.