Novel T-shape three-coordinate nickel(I) chlorides bearing an N-heterocyclic carbene ligand, NiCl(IPr)(2) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene), were isolated by a reaction of Ni(0)(NHC)(2) with aryl chlorides. This Ni(I) complex was shown to act as a catalyst in a cross-coupling reaction of aryl halides with phenylmagnesium chloride.