Surface chemistry information is crucial in understanding catalytic and sensing mechanisms. However, resolving the outermost monolayer composition of metallic nanoporous materials is challenging due to the high tortuosity of their morphology. In this study, we first elaborate on the capabilities and limitations of atom probe tomography (APT) in resolving interfaces. Subsequently, an electrochemical approach is designed to characterize the surface composition of nanoporous gold (NPG), developed from dealloying an inexpensive precursor (95 at. % Ag, 5 at. % Au), by the means of aqueous electrochemical measurements of the selective electrosorption of sulfide ions, which react strongly with Ag, but to a significantly lesser extent with Au. Accordingly, cyclic voltammetry was performed at various scan rates on NPG in alkaline aqueous solutions (0.2 M NaOH; pH 13) in the presence and absence of 1 mM Na2S. Calibrations via similar voltammetric measurements on pure polycrystalline Ag and Au surfaces allowed for a quantitative estimation for the Ag surface coverage of NPG. The sensitivity threshold for the detection of the adsorbate–Ag interaction was assessed to be approximately 2% Ag surface coverage. As curves measured on NPG only showed featureless capacitive currents, no faradaic charge density associated with sulfide electrosorption could be detected. This study opens a new avenue to gain further insight into the monolayer surface coverage of metallic nanoporous materials and assists in enhancement of the interpretation of APT reconstructions.