Classical application of ion-selective membranes is limited to either electrochemical or optical experiments. Herein, the proposed ion-selective membrane system can be used in both modes; each of them offering competitive analytical parameters: high selectivity and linear dependence of the signal on logarithm of analyte concentration, high potential stability in potentiometric mode, or applicability for alkaline solutions in optical mode. Incorporation of analyte ions into the membrane results in potentiometric signals, as in a classical system. However, due to the presence of lipophilic positively charged ions, polymer backbones, full saturation of the membrane is prevented even for long contact time with solution. The presence of both positively charged and neutral forms of conducting polymers in the membrane results in high stability of potential readings in time. Optical signal generation is based on polythiophene particulates dispersed within the ion-selective membrane as the optical transducer. An increase of emission is observed with an increase of analyte contents in the sample.