In this work, construction and analytical application of a new potentiometric PVC membrane sensor for the determination of Clomiphene are studied. The sensor respond based on ion-exchange mechanism between the organic layer of the membrane and aqueous phase. The proposed sensor showed a linear dynamic range between 8.0×10-6 and 1.0×10-2 mol L-1 of Clomiphene with a Nernstian slope of (57.6±0.6) mV decade-1 and a detection limit of 6.3×10-6 mol L-1. The best PVC membrane sensor response was obtained by a membrane composition of 30% PVC, 62% DBP, 6% ion-pair and 2% ionic liquid. The potentiometric response was independent to the solution pH in the range of 4.0 to 6.0. The proposed electrode displayed fast response time about 15 s, and it can be used for a period of six weeks without any considerable change in its performance. Application of this potentiometric sensor for the Clomiphene determination in some pharmaceutical formulations was satisfactory results.