The extraction of silver from aqueous thiocyanate-perchlorate solutions using diphenyl-2-pyridylmethane (DPPM) in benzene has been investigated. The variables such as concentrations of perchloric acid, thiocyanate and DPPM influencing the extraction have been optimized. Maximum extraction has been achieved from 0.01 M perchloric acid solution containing 0.01 M potassium thiocyanate in 0.075 M DPPM in benzene. The extraction was found to be independent of silver concentration in the range from 10−4–10−6 M. The influence of several anions on the extraction was examined; only thiosulphate interfered seriously and reduced the extraction below 1%. Thus 0.1M potassium thiosulphate was found to back-extract silver quantitatively in one step. Under selected optimal conditions, very small extraction ( 99%). This extraction procedure can be used for the preconcentration of silver and tin or their separation from rare earths mentioned above.