Some new inorganic phosphoylating agents for the synthesis of biophosphates are reviewed. The advantages of diphosphonate and trimetaphosphate in the selective phospohrylation and prebiotic condensation of amino acids are described. Reaction mechanisms of the selective phosphorylation are discussed. Significant role of a five-membered cyclic mixed anhydride intermediate in the prebiotic peptide bond formation is described by using a recent experimental evidence obtained by our research group.