An electrolysis technique at a constant potential was used to develop a highly reproducible and fast elaboration method of adherent manganese dioxide thin films on a glassy carbon electrode from aqueous solutions containing sulfuric acid and manganese sulfate. The resulting films were found to have a nanostructured character presumably due rather to birnessite (δ-MnO2) than to γ-MnO2, as suggested by their Raman and XRD signatures. They lead to modified electrodes that present an obvious although complex pH dependent potentiometric response. This sensor indeed showed a single slope non-Nernstian linear behaviour over the 1.5–12 pH range for increasing pH direction (“trace”), whereas a Nernstian two slopes linear behaviour was observed for decreasing pH direction (“re-trace”). Preliminary EIS experiments carried out at a pH value of 1.8 seem to reveal a sensitivity mechanism based on proton insertion process at least at highly acidic pH values.