A highly efficient P-H insertion of α-imino copper carbene into H-phosphine oxides, leading to 3-phosphinoylindoles with a broad substrate diversity and good chemoselectivity, is established. This methodology provides a rapid and efficient approach for the C (sp2)-P bond formation via the P-H insertion strategy. The stereoselective P-H insertion of α-imino copper carbene represents a unique example of asymmetric P-H insertion, affording P-stereogenic 3-phosphinoylindoles with high stereoselectivities.