We performed a series of distance tunneling characteristics measurements for the system Au(111)/0.05 M H2SO4 + 1 mM Cu2+ in the absence and in the presence of small amounts of chloride to understand if it is possible to map the liquid part of the double layer perpendicular to the electrode surface. We found that we probed the double layer in a distance range where we do not penetrate into the inner Helmholtz layer. Nevertheless, the tip is sufficiently close to the metal surface to address adlayer features showing sensitivity toward long-range-ordered structures. The bias between the scanning tunneling microscope tip and the sample drops in the inner Helmholtz layer, and strong electronic overlap exists between the adsorbed layer and the metal surface. A detailed analysis showed that our approach is capable of detecting molecular contributions to the electronic structure of ordered adlayers. At larger distances from the surface, the average barrier height was found to be about 1 eV, practically independent of the electrode potential. Our results represent a further step to advance the application of scanning tunneling spectroscopic methods in electrochemistry and open up a new, exciting field of studying not just the structure and electronic properties but also the reactivity of adsorbed adlayers at the atomic level.