Treatment of heteroscorpionate zinc benzyloxy complex LZnOBn (1, L = (MePz)2CP(Ph)2NPh,MePz = 3,5-dimethylpyrazolyl) with phenylsilane (PhSiH3) gave a zinc hydride complex LZnH (2) containing a rare terminal hydride fragment. X-ray diffraction analysis and the DFT calculation confirm the zwitterionic structure of complex 2. The stoichiometric reaction of 2 with CS2 readily afforded a dithioformate complex LZnSCH(S) (3) of the C═S insertion into the Zn–H product. Moreover, complex 2 was an efficient catalyst for the hydrosilylation reaction of a series of silanes and aldehydes under mild conditions, featuring excellent functional group tolerance. The preliminary mechanistic study revealed that both zinc benzyloxy complex 1 and zinc hydride complex 2 were involved in the hydrosilylation process as the reaction intermediates.