The sulfide podand (an open-chain neutral mutlidentate ligand with six sulfur donor atoms) 1,12-di-2-thienyl-2,5,8,11-tetrathiadodecane (TTD) was synthesized. Its extracting properties were examined with 1,2-dichloroethane and 4-methylpentan-2-one as solvents. The reagent showed high selectivity for silver(I) and copper(I) ions; mercury(II) was extracted (ca. 97%) under certain conditions. Extraction of silver(I) was studied in detail with 110mAg tracer. Log D values ⩾2 were obtained for the range from pH 6 (with perchlorate as counter-ion) to 2 M perchloric acid or 6 M nitric acid. The ratio of Ag:TTD in the complex was 1:1. Silver could be back-extracted with 4–6 M hydrochloric acid.