A new method to establish the absolute configurations of organic compounds is reviewed. This method is designated “axial chirality method” because it uses axially chiral biaryls as chiral auxiliaries. Chiral secondary alcohols, α-chiral primary amines and α-chiral carboxylic acids are derivatized with the above reagents. The absolute configurations of original compounds are correlated to the Δδ values, which are defined as Δδ=δaS-δaR for each proton of the diastereomeric derivatives. Some models are described to explain the observed proton shifts and the signs of δas In certain cases, NOEs were observed between the protons of the reagent's moiety and those of substrate's one. The absolute configuration of a sterically hindered tertiary alcohol was determined by this new method using the Δδ values and NOE correlations. One new C-centrochiral reagent was also presented. Versatility and limitation of this method are discussed.