A new silver mediated aminophosphinoylation of propargyl alcohols with aromatic amines and H-phosphine oxides for the construction of α-aminophosphine oxides has been developed. The C--N and C--P bond could be efficiently formed in one pot operation via sequential C--C and C--O bond cleavage of propargylic alcohols. This present methodology, which not only provides a simple and altative strategy for the synthesis of α-aminophosphine oxides, but also opens a new window for the cleavage reactions of propargyl alcohols via dealkynalation coupling.