An unusual β-elimination reaction involving zinc(II) and LiCl is reported. LiCl and a coordinatively saturated disilazido zinc compound form an adduct that contains activated SiH moieties. In THF/toluene mixtures, this adduct is transformed into a zinc hydride and 0.5 equiv. cyclodisilazane. The Li+ and Cl− ions apparently affect the reaction pathway of the disilazido zinc in a synergistic fashion. Thus, the zinc hydride and cyclodisilazane products of formal β-elimination are not observed upon treatment of the zinc disilazide with Cl− or Li+separately.