Catalytic C–P and N–P bond formation via double hydrophosphorylation of nitriles with diphenylphosphane oxide using alkali metal precatalyst [MN(SiMe 3 ) 2 ] (M = Li, Na, K) is reported. The potassium congener was observed to be the most efficient catalyst for converting aryl nitriles to the corresponding N-((diphenyl-phosphoryl)(aryl)methyl)-P,P-diphenylphosphinic amide [ArCHP(O)-Ph 2 NHP(O)Ph 2 ] at mild temperature (60 °C) and with neat reactants. Double hydrophosphorylation of alkynes with HP(O)Ph 2 is also very effective when [KN(SiMe 3 ) 2 ] is used as a precatalyst at room temperature and gives the corresponding 1,2-diylbis(diphenyl-phosphane oxide [RCHP(O)Ph 2 CH 2 P(O)Ph 2 ] as the product. A wider substrate scope of both reactions is explored. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim