A copper catalyst bearing a suitable Xantphos derivative or NHC ligand was found to be highly efficient for the selective semihydrogenation of non-polar unsaturated compounds using a mixture of a silane and an alcohol as reducing agent. The catalytic system was useful for the selective semihydrogenation of internal alkynes to (Z)-alkenes with suppression of overreduction to the corresponding alkanes. Furthermore, semihydrogenations of terminal alkyne, 1,2-diene, 1,3-diene, 1,3-enyne and 1,3-diyne systems were also achieved selectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.