The electronic structure at the interface of chalcogenide/metal hybrid nanostructure (CdSe–Au tipped) had been studied by UHV scanning tunneling spectroscopy (STS) technique at room temperature. This nanostructure was synthesized by a phase transfer chemical method. The optical absorption of this hybrid nanostructure was recorded, and the application of the effective mass approximation (EMA) model gave dimensions that were confirmed by the direct measurements using the scanning tunneling microscopy (STM) as well as the high-resolution transmission electron microscope (HRTEM). The energy band gap obtained by STS agrees with the values obtained from the optical absorption. Moreover, the STS at the interface of CdSe–Au tipped hybrid nanostructure between CdSe of size about 4.1 ± 0.19 nm and Au tip of size about 3.5 ± 0.29 nm shows a band bending about 0.18 ± 0.03 eV in CdSe down in the direction of the interface. Such a result gives a direct observation of the electron accumulation at the interface of CdSe–Au tipped hybrid nanostructure, consistent with its energy band diagram. The presence of the electron accumulation at the interface of chalcogenides with metals has an important implication for hybrid nanoelectronic devices and the newly developed plasmon/chalcogenide photovoltaic solar energy conversion.