The performance of octahydroxycalix[4]arene derivative used as a neutral carrier for silver polymeric membrane electrode was studied. The sensor gave a good Nernstian response of 58 ± 1 mV per decade for silver ion in the activity range 3.3 × 10^-6 to 3.3 × 10^-2 M Ag⁺. The limit of detection reached 2.1 × 10^-6 M Ag⁺ and exhibited high selectivity for silver ion against the alkali, alkaline earth and transition metal ions. The sensor can be used in wide pH range from 1.5 to 6.5. The response time of the sensor is less than 20 s. The potentiometric sensor was used as the indicator electrode in the titration of Ag⁺ ions by sodium chloride solution.