Ion exchange and cementation experiments were done to separate silver(I) from a raffinate containing silver(I), nickel(II), and zinc(II) and small amounts of copper(II) and tin(II). The raffinate resulted from the recovery of gold(III), tin(II) and copper(II) by solvent extraction from a leaching solution of anode slime. Ion exchange with anionic resins was not effective in separating silver(I) because tin(II) and zinc(II) were selectively adsorbed into the anionic resins. It was possible to separate silver(I) by cementation with copper sheet. Treatment of the cemented silver with nitric acid solution increased the purity of silver(I) in the solution from 50.9% to 99.99%. Adjusting the pH of the AgNO3 solution to higher than 6, followed by adding ascorbic acid as a reducing agent, led to the synthesis of silver particles with micron size.