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Recent progress in the generation of ultrashort XUV-pulses by means of high harmonic generation provides a means to monitor the dynamics of surface chemical reactions using photoemission spectroscopy. In this paper we describe details of an experimental setup for time-resolved photoemission spectroscopy using high harmonic generation. We also present results where the different steps involved in the laser-induced change of an adsorbate–surface bond were monitored with sub-100 femtosecond time-resolution. [Copyright &y& Elsevier]