[reaction: see text] An N-heterocyclic carbene copper chloride (NHC-CuCl) complex (2) has been prepared and used to catalyze the conjugate reduction of alpha,beta-unsaturated carbonyl compounds. The combination of catalytic amounts of 2 and NaOt-Bu with poly(methylhydrosiloxane) (PMHS) as the stoichiometric reductant generates an active catalyst for the 1,4-reduction of tri- and tetrasubstituted alpha,beta-unsaturated esters and cyclic enones. The active catalytic species can also be generated in situ from 1,3-bis(2,6-di-isopropylphenyl)-imidazolium chloride (1) CuCl(2).2H(2)O in the presence of NaOt-Bu and PMHS.