Commercially available compound ZnEt₂ acts as an efficient precatalyst for the solvent-free hydrophosphinations of heterocumulenes using Ph₂PH as reagent. As far as we knew, this has been not reported in group 12 metal catalyzing reactions. A suggested mechanism of this reaction is explored, and the intermediate [{Ph₂PC(NⁱPr)₂}ZnEt]₂ is obtained and characterized by a single-crystal X-ray structural analysis.