A new methodology was applied for the designing potentiometric membrane sensors. An electrochemically polymerized Poly(Pyrrole)s (PPy) film was applied as a solid contact-ion to electron transducer on the surface of a pencil graphite electrode (PGE) to make an all-solid-state ion selective electrode (CP-ASS-ISE) for the determination of Tramadol Hydrochloride. A thin layer of a PVC membrane containing synthesized ion-pair as the active element and suitable plasticizer was then placed on the surface of the conducting polymer layer to prepare the sensor. The suggested sensor showed a Nernstian response (a slope of 57.17 mV per decade) over the concentration range of 1.0×10 −6 to 1.0×10 −1 mol L -1 . The Tramadol sensor had a low detection limit of 7.4×10 −7 mol L -1 with response time of less than 10s in the concentrated solutions. The working pH range of the sensor was 2.0-7.0. Finally, the proposed sensor used for the Tramadol assay in some pharmaceutical tablets.