Abstract A rapid, efficient, solvent-free, and catalyst-free procedure has been developed for the synthesis of pseudohalophosphates from phosphorochloridate and sodium (or potassium) pseudohalides under microwave irradiation. Diethyl, diisobutyl, and diphenyl phosphorazidates, phosphorocyanidates, and phosphor (isothiocyanidate) s 2a–2i were prepared in good yields under mild conditions.