The degradation of sulfacetamide with the formation of sulfanilamide leads to a deterioration in the quality of pharmaceuticals. In this work, potentiometric sensors for the simultaneous determination of sulfanilamide, sulfacetamide and inorganic ions, and for assessing the degradation of pharmaceuticals were developed. A multisensory approach was used for this purpose. The sensor cross-sensitivity to related analytes was achieved using perfluorosulfonic acid membranes with poly(3,4-ethylenedioxythiophene) or polyaniline as dopants. The composite membranes were prepared by oxidative polymerization and characterized using FTIR and UV-Vis spectroscopy, and SEM. The influence of the preparation procedure and the dopant concentration on the membrane hydrophilicity, ion-exchange capacity, water uptake, and transport properties was investigated. The characteristics of the potentiometric sensors in aqueous solutions containing sulfanilamide, sulfacetamide and alkali metals ions in a wide pH range were established. The introduction of proton-acceptor groups and π-conjugated moieties into the perfluorosulfonic acid membranes increased the sensor sensitivity to organic analytes. The relative errors of sulfacetamide and sulfanilamide determination in the UV-degraded eye drops were 1.2 to 1.4 and 1.7 to 4%, respectively, at relative standard deviation of 6 to 9%.