The interfacial behavior of the single quantum well (SQW) GaAs/AlxGa1−xAs electrode in HQ/BQ and Fc/Fc+ electrolytes was characterized respectively by studying the quantum confined Stark effect and Franz-Keldysh oscillation with electrolyte electroreflectance spectroscopy. The interaction of the surface state of the SQW electrode with redox species and its effects on the distribution of external bias at the interface of the SQW electrode are discussed.