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Cu-based catalysts represent a powerful tool for a variety of synthetic transformations, including arylation of nucleophiles, alkyne coupling, dipolar cycloadditions, Diels-Alder reactions, oxidations, condensations and enantioselective reactions. The use of water as reaction medium for these procedures is currently emerging as a very active research field. The present Review focuses on the more synthetically useful “on water” Cu-mediated processes, in which organic co-solvents are absent (or present in negligible amount), and covers the literature until the end of 2009.