A highly selective silver (I) electrode was prepared by incorporating 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix 5) as a neutral ionophore into plasticized polyvinylchloride (PVC) membrane. The best response characteristic was obtained using the composition dibutyl phthalate (DBP) : PVC : sodium tetraphenyl borate (NaTPB) : kryptofix 5 in the percentage ratio of 60.2 : 30 : 4.5 : 5.3 (w:w, mg). The electrode exhibits a Nernstian slope (60.1 +/- 0.4 mV/decade) in a wide linear concentration range of 1.0 x 10(-6) to 1.0 x 10(-1) M. The detection limit of the electrode is 9.02 x 10(-7) M. The electrode has a fast response time of about 15 s, with a satisfactory reproducibility and relatively long life time of about 7 weeks without significant drift in potential. The electrode operates in the wide pH range of 2.0-7.0. This electrode reveals a very good selectivity toward Ag+ ion over a wide range of alkali, transition and heavy metal cations. The electrode was used as an indicator electrode for potentiometric titration of Ag+ using sodium chloride solution with a sharp potential change occurred at the end point. The proposed electrode also was applied for the direct determination of Ag+ cation in doubly distilled deionized water samples spiked with different concentrations of silver (I) cation. (C) 2012 The Electrochemical Society. [DOI:10.1149/2.113204jes] All rights reserved.