The ion-to-electron transduction reaction mechanism at the buried interface of the electrosynthesized poly(3-octylthiophene) (POT) solid-contact (SC) ion-selective electrode (ISE) polymeric membrane has been studied using synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), and electrochemical impedance spectroscopy (EIS)/neutron reflectometry (NR). The tetrakis[3,5-bis(triflouromethyl)phenyl]borate (TFPB(-)) membrane dopant in the polymer ISE was transferred from the polymeric membrane to the outer surface layer of the SC on oxidation of POT but did not migrate further into the oxidized POT SC. The TFPB(-) and oxidized POT species could only be detected at the outer surface layer (≤14 Ǻ) of the SC material, even after oxidation of the electropolymerized POT SC for an hour at high anodic potential demonstrating that the ion-to-electron transduction reaction is a surface confined process. Accordingly, this study provides the first direct structural evidence of ion-to-electron transduction in the electropolymerized POT SC ISE by proving TFPB(-) transport from the polymeric ISE membrane to the oxidized POT SC at the buried interface of the SC ISE. It is inferred that the performance of the POT SC ISE is independent of the thickness of the POT SC but is instead contingent on the POT SC surface reactivity and/or electrical capacitance of the POT SC. In particular, the results suggest that the electropolymerized POT conducting polymer may spontaneously form a mixed surface/bulk oxidation state, which may explain the unusually high potential stability of the resulting ISE. It is anticipated that this new understanding of ion-to-electron transduction with electropolymerized POT SC ISEs will enable the development of new and improved devices with enhanced analytical performance attributes.