Novel chiral derivatising agents (CDAs) such as methyl itaconate–anthracene adducts (MIAs) were reported for the absolute configuration determination of chiral secondary alcohols by the ¹H NMR technique. These adducts were facilely prepared through well-known reactions, and furthermore, commercially available starting materials. According to these synthetic routes, the desired MIAs were afforded in 6 steps with 49% overall yield from dimethyl itaconate. Moreover, the represented MIAs provided significantly large differences of chemical shift values (Δδ^SR). No racemisation from the tertiary characteristics of the adjacent alpha carbon was observed.