The presence of radiogenic osmium-187 formed by beta-fission of rhenium-187 is the specific characteristic of some rhenium-containing sources. The technology for the recovery of rhenium and osmium from sulfuric acid scrub solutions formed by wet gas purifying in pyrometallurgical processing of sulfide polymetallic ores was developed. The technology based on solvent extraction following preliminary conversion of the metals into the optimal chemical species. The technology ensures quantitative recovery, concentration and separation of rhenium and osmium, production commercially viable concentration of elements.