Nanophysics at electrochemical interfaces, probing the physical properties of nanostructures, requires laterally resolved in-situ spectroscopy, in particular voltage tunneling spectroscopy (VTS), which is at present not yet established. In-situ spectroscopy is required to achieve reliable and reproducible measurements of the intrinsic properties of nanostructures in an electrochemical environment, which are mainly determined in small nanostructures by surface atoms rather than bulk atoms. In contrast to tunneling spectroscopy in ultrahigh vacuum, tip and substrate double-layer capacitances as well as Faradaic currents play an important role in voltage tunneling spectroscopy at electrochemical interfaces. Deoxygenation of the electrolyte, fast measurements using appropriate instrumentation, and minimization of the unisolated tip apex and substrate surface areas exposed to the electrolyte are the key parameters to achieve reliable in-situ voltage tunneling spectroscopy data at electrochemical interfaces. The presented data show that bias voltage intervals of more than 1000 mV can be utilized for spectroscopic investigations in aqueous electrolytes, which allow the in-situ study of discrete electronic levels in nanostructures.