One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-γ-benzyl- l-glutamate (PBLG)/CDCl 3 solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the 1H detection. On the other hand in the present study the benefit is derived from the presence of several couplings among the entire network of interacting protons. Transition selective 1D 1H– 1H correlation experiment (1D-COSY) which utilizes the coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton–proton couplings of an enantiomer within a short experimental time (few minutes).