Trident molecules containing pyridyl groups have been prepared for use as novel extraction reagents to investigate their physico-chemical properties for dissolution into the aqueous phase and their ability, together with their corresponding monomeric analogues, to extract precious metal ions. Differences in their behavior were related to the pK(a) values of the trident molecules and the position of the nitrogen atom in the pyridyl groups. The trident molecules exhibit the ability to selectively extract silver from mixtures of other precious metals. The extraction mechanism and the coordination site of the silver ion with a 2-pyridyl derivative were determined by slope analysis and peak shift of the H-1-NMR spectra of the extraction reagent before and after silver loading.