Homopolypeptide‐based alignment media can induce different orientations of enantiomers as a result of their α‐helical structures. This property enables the discrimination of enantiomers through anisotropic NMR parameters such as residual dipolar couplings (RDCs). In this paper, the enantiodiscriminating properties of two alignment media derived from polyglutamic acid derivatives – poly‐γ‐benzyl‐L‐glutamate (PBLG) and poly‐γ‐ethyl‐L‐glutamate (PELG) – are compared and discussed. The two analytes, isopinocampheol and β‐pinene, are investigated, and the role of the lateral side chain of the homopolypeptide in the orientation process is examined.