In recent years, research on organophosphorus compounds, particularly phosphoramidates PRA and phosphonamides PNA, has attracted the attention of scientists because of the manifold applications of PCR and PNA. They are formally derived from phosphoramidic acids O = P(OH)(NR2)2, O = P(OH)2(NR2) and phosphonamidic acids R-PO(OH)(NR2)2 by substitution of OH for NR2. Numerous reviews dedicated to phosphoramides and phosphonamides have been published. The purpose of this current review is to present different synthetic methodologies for the synthesis of phosphoramidates and phosphonamides by use of conventional approaches or alternative strategies under green chemistry conditions. Besides the syntheses, the corresponding reaction mechanisms and applications of these compounds are discussed.