The prediction of the absolute configuration of chiral alcohols, namely phenylcarbinols, from the 31P NMR spectra of the diastereoisomers obtained with organophosphorus diamino-derivatizing agents is presented. A simplified model based on NMR and crystallographic data is given, which associates the spatial location of the substituents of the stereogenic alcohol centre with the sign of the ?d(R-S) (?d(R-S) representing the chemical shift difference between two diastereoisomers of the CDAs and the chiral secondary alcohol).