Facilitated transport of silver(I) cation across a bulk liquid membrane by two synthesized ligands, bis-β-enamino ester (BBEE) and bis(benzoic acid) trioxaheptane (BBAT), as carriers dissolved in dichloromethane has been investigated. BBEE was used as a specific ion carrier for the transport of silver(I) ion. The influence of experimental parameters affecting the transport efficiency of silver(I) ion have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the receiving phase and picrate ion as ion pairing agent in the source phase, the amount of silver(I) ion transported across the liquid membrane after 120 min was found to be 97%. Tolerance to the presence of different ions was investigated and it was found that silver(I) cation transport was not affected even in the presence of 10-fold concentration of these metal cations in solution. This system was applied for the recovery of silver(I) cation from silver plating and photographic waste solution.