A new PVC-membrane electrode for $Ag^+$ ion based on a thia-substituted macrocyclic diamide has been prepared. The electrode exhibited a Nernstian response for $Ag^+$ over a wide concentration range $(1.7{ imes}10^{-6}-1.0{ imes}10^{-1}M)$. It has a response time <15 s and can be used for at least 3 months without divergence. The proposed membrane sensor revealed good selectivities for $Ag^+$ over a variety of metal ions and can be used in a pH range 3.0-7.5. It has been used successfully for direct determination of $Ag^+$ in different real samples and, as an indicator electrode, in the titration of silver ion.