Nanosize gold clusters were grown by thermal evaporation on ultrathin magnesia films on Mo(100) and investigated by femtosecond (fs)-laser photoemission spectroscopy. The surface work function in this system was found to increase with increasing nominal gold coverage. Methyl bromide (CH 3 Br) molecules adsorb molecularly on the magnesia surface as well as on the gold clusters. At sub-monolayer coverage the CH 3 Br molecules were, however, considerably stronger bound to the gold particles than to the magnesia surface as revealed by temperature programmed desorption spectroscopy. To investigate the photoreaction dynamics of the adsorbate molecules fs-laser pump-probe mass spectrometry was applied. In this new approach the methyl fragment appearance was monitored after photoexcitation of the adsorbed CH 3 Br with fs time resolution. The transient methyl data revealed that the CH 3 Br dissociation and subsequent methyl desorption proceeded in less than one picosecond. Most interestingly, a part of the transient signal could be unambiguously assigned to the dynamics of methyl desorption from the gold clusters. The appearance of this signal at about 270 fs after photoexcitation illustrates the massive distortion of the CH 3 Br electronic level structure due to the strong interaction with the gold clusters compared to the bare magnesia surface.