AbstractAn amidoalkylation of PCl3or its organic derivatives in acetic acid solution takes place because equilibrium between AcOH and exist, leading to hydroxychlorophosphines. Those last compounds undergo an amidoalkylation like other nucleophiles. Based on these data, it was shown that an amidoalkylation reaction is usual for all phosphorus compounds with the R2P(O)H system and provides derivatives with the functions. The scope and limitation of these reactions are discussed.