The construction and electrochemical response characteristics of poly(vinyl chloride) matrix ion-selective electrodes (ISEs) for dextromethorphan (DXM) hydrobromide are described. The membranes incorporate ion-association complexes of DXM with reineckate salt {[Cr(NH3)2(SCN)4]NH4} or phosphomolybdic acid [H3(PMo12O40)], as electroactive materials and dioctylphthalate or dibutylsebacate as a plasticizing solvent mediator. The sensors display a fast, stable and linear response with slopes of 54.4 to 59.5 mV/decade at pH 2.5 -6.5 and a detection limit of 1.0 ¥ 10 -6 M. Moreover, the sensors exhibit very good selectivity for DXM over opiate alkaloids, as well as organic and inorganic cations. The sensors proved to be useful for the determination of 5.0 ¥ 10 -5 -1.0 ¥ 10 -3 M DXM hydrobromide in pure as well as in dosage forms by direct potentiometry and standard addition methods. Determination of 5.0 ¥ 10 -4 M DXM using the standard addition method and a sensor based on phosphomolybdate and dioctylphthalate shows an average recovery of 99.8% and a relative standard deviation (RSD) of 0.4%.