A new highly selective silver(Ⅰ) electrode was prepared with a PVC membrane using 5,10,15-tris(pentafluorophenyl)corrole as an electroactivematerial, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive in the percentage ratio of 3∶3∶62∶32 (corrole∶NaTPB∶o-NPOE∶PVC, w∶w). The electrode exhibited linear response with a near Nernstian slope of 54.8 mV/decade within theconcentration range of 5.1×10−6 to 1.0×10−1Msilver ions, with a working pH range from 4.0 to 8.0, and a fast response time of <30 s. Selectivitycoefficients for Ag(Ⅰ) relative to a number of interfering ions were investigated. The electrode is highly selective for Ag(Ⅰ) ions over a large numberof mono-, bi-, and tri-valent cations. Common interferents like Hg2+ and Cd2+ show very low interfering effect on the silver assay, which is valuableproperty of the proposed electrode. Several electroactive materials and solvent mediators have been compared and the experimental conditionswere optimized. The sensor was applied to the determination of silver in real ore samples with satisfied results.