The construction and application of a high‐vacuum deposition system housed in a recirculating, catalytically scrubbed, inert‐atmosphere glove box is reported. This system is specifically applied to the fabrication of tunnel diodes used in a surface vibrational spectroscopy called inelastic electron tunneling spectroscopy or IETS. Through the use of this inert‐atmosphere adsorption/fabrication system, tunneling spectra have been obtained from a variety of air‐sensitive compounds adsorbed on aluminum oxide. Up to now, spectra of some of the species reported here have been unattainable by the adsorption techniques used in IETS. The test molecules employed in this study included TCNE (tetracyancethylene), TCNQ (tetracyanoquinodimethane), and Co2(CO)8. TCNE adsorbed reactively on thin‐film alumina under nitrogen to form a species with a vibrational spectrum similar to that of the TCNE−2ion, while TCNQ appears to form the monoanion under the same adsorption conditions.