Modeling of polystyrenes (PS) with various stereosequences in the narrow cylindrical channels corresponding to those found in gamma-cyclodextrin inclusion compounds (CD ICs) has been conducted. Based on the conformational modeling of stereoisomeric polystyrenes (PSs) in narrow channels, it was suggested that polystyrene with unusual microstructures might be produced by the constrained polymerization of styrene monomer in its gamma-CD-IC crystals. The in-situ polymerization of styrene inside the narrow channels of its gamma-CD-IC crystals was performed in both organic and aqueous media. The C-13 NMR spectrum of PS synthesized inside the gamma-CD channels in an aqueous medium shows some differences when compared to the C-13 NMR spectrum of PS synthesized in toluene. These are presumably because of differences in their stereosequences. Here, we report our preliminary findings.