Catalytic ring-opening phosphonation and phosphatation of vinyl aziridines have been developed in a regiodivergent fashion, giving linear and branched products. Generation of P-centered radicals enables SN2'-type ring-opening reactions of vinyl aziridines to afford δ-amino alkylphosphorus products at room temperature. On the other hand, in situ generated phosphate anions via the Ag-catalyzed aerobic oxidation of phosphonyl reactants underwent SN2 reaction to provide branched phosphorus-containing amine products. Furthermore, this divergent methodology serves as a powerful tool for the stereospecific synthesis of phosphorus-containing amino acid derivatives.