Derivatization of mixtures of enantiomers (including racemates) of chiral secondary alcohols with a pure enantiomer of the auxiliary reagent, 9-anthrylmethoxyacetic acid [( R)- or ( S)-9-AMA)] followed by directly coupled HPLC–NMR of the mixture of the esters allows separation of the two enantiomers, the determination of the e.e. and the assignment of their absolute configuration in a single operation and with just a few micrograms of substance. The procedure can also be applied to the assignment of the absolute configuration of a single enantiomer of the alcohol.