Polymer prepared from a monomer ((S)-configuration at stereogenic center) in a cholesteric liquid crystal (CLC) medium consisting of chiral molecules in (R)-configuration, a three-dimensional (3D) chiral continuum, exhibits intense Cotton effect compared to polymer prepared in the CLC with (S)-configuration. This result can be explained by intermolecular interaction between the monomer and the CLC medium in the polymerization process. The intramolecular twisted structure along the polymer chain (secondary structure) and the helical aggregation between the polymer chains (intermolecular structure and tertiary structure) induced by the liquid crystal medium as 3D chiral continuum are discussed. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013