In this work, C(60) fullerene is used as an electrochemical mediator for the development of an all-solid-state ISE. The unique electrochemical characteristics of the fullerenes allow for the facile ion-to-electron transduction across the ionically active polymeric ion-selective membrane and the electrochemically active glassy carbon transducer. The interfacial ion-to-electron charge transfer was investigated by Electrochemical Impedance Spectroscopy. The study of the analytical characteristics of a model potassium-selective electrode, together with the EIS studies, reveals that, indeed, the interfacial C(60) electrochemically active layer facilitates the ion-to-electron transduction, providing a stable and reversible solid-state ISE system. This finding is a significant contribution to the efforts aiming at overcoming one of the most significant drawbacks of the solid-state ISEs, that is the potential drift observed during continuous measurements, and could lead to the development of both cation- and anion-sensitive systems.