Electronic structure induced by adsorbates at the interface of Al/AlOx/Au tunnel junctions has been observed by elastic electron tunneling spectroscopy. Strong structures appearing in the tunneling spectra above ∼1 eV after exposure to I, Hg, Bi, and organohalides, have been interpreted in terms of adsorbate‐induced surface states. The spectroscopic capabilities of elastic electron tunneling spectroscopy may be useful in the area of chemical detection. In the broader sense, the observation of adsorbate‐induced unoccupied electronic states below the vacuum energy, makes elastic electron tunneling spectroscopy a potentially useful technique for the study of surfaces.