Carbon monoxide (CO) adsorption properties of Pd/Al systems have been studied using X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS) and static secondary ion mass spectroscopy (SSIMS) under UHV conditions. Measured XPS and TDS spectra were compared to that of clean bulk metals (Pd, Al). Pd adlayers, prepared by vacuum evaporation onto a pure polycrystalline Al surface, exhibited a strong interaction with Al atoms resulting in formation of a Pd-Al alloy of a noble metal-like electronic structure. The shifts of the Pd 3d core levels and the Pd 4d-band centroid toward higher binding energies due to bimetallic bond formation were observed. The CO TDS spectra consisted of two desorption peaks, both lying lower than the one typical for a Pd foil, indicating distinct weakening of the Pd-CO chemisorption bond. Partial CO dissociation on the Pd/Al surface during adsorption/desorption cycles, accompanied by CO, and H2O production, was observed. CO dissociation caused creation of Pd-C and Al-O chemical bonds on the Pd/Al surface resulted in weakening of the Pd-Al bimetallic bond. © 2004 Elsevier B.V. All rights reserved.