Nickel joins the fairly exclusive list of metals that can activate nitrile C-H bonds. We report the first example of the C-H activation of an acetonitrile ligand on a nickel center. The acetonitrile ligand formally loses a proton and undergoes a sharp flip to give a cyanomethyl ligand that is coordinated to the nickel atom. Structures of an initial N-bound acetonitrile-nickel complex and of a final cyanomethyl-nickel complex are both presented.