Nuclear magnetic resonance spectroscopy has been performed on xenon adsorbates on a iridium single crystal surface. Optical pumping methods have been applied to increase the Xe-129 polarization and thus the NMR sensitivity by five orders of magnitude. Enriched Xe-121 gas has been adsorbed on a carbon monoxide and ethylidyne covered Ir(1 1 1) surface with coverages up to one monolayer. In addition the surface of a condensed xenon bulk has been investigated. Narrow resonances with distinct chemical shifts were observed reflecting the very different nature of the substrates. This opens a new field of spectroscopy for the study of surfaces. (C) 2003 Elsevier Science B.V. All rights reserved.