A novel series of side-chain liquid crystalline copolysiloxanes containing [S]-1-(2-naphthyl) ethyl 6-[4-(10-undecen-1-yloxy) biphenyl-<svg style="vertical-align:-0.0pt;width:12.4375px;" id="M1" height="17.7125" version="1.1" viewBox="0 0 12.4375 17.7125" width="12.4375" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"> <g transform="matrix(.017,-0,0,-.017,.062,17.65)"><path id="x34" d="M456 178h-96v-72q0 -51 12.5 -62.5t72.5 -16.5v-27h-256v27q65 5 78 17t13 62v72h-260v28q182 271 300 426h40v-407h96v-47zM280 225v295h-2q-107 -148 -196 -295h198z" /></g> <g transform="matrix(.012,-0,0,-.012,8.225,9.488)"><path id="x2032" d="M227 744l-123 -338l-31 15l73 368q12 3 41.5 -8t36.5 -20z" /></g> </svg>-carbonyloxy]-2-naphthoate mesogenic and 4-biphenyl <svg style="vertical-align:-0.0pt;width:12.4375px;" id="M2" height="17.7125" version="1.1" viewBox="0 0 12.4375 17.7125" width="12.4375" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"> <g transform="matrix(.017,-0,0,-.017,.062,17.65)"><use xlink:href="#x34"/></g> <g transform="matrix(.012,-0,0,-.012,8.225,9.488)"><use xlink:href="#x2032"/></g> </svg>-allyloxybenzoate mesogenic side groups in the backbone and side chains liquid crystalline copolymers were prepared and evaluated as possible stationary phases for gas chromatography capillary columns. All copolymers display enantiotropic cholesteric phases. These mesomorphic polysiloxanes specimens with the widest temperature range were used as the stationary phase in a gas chromatography capillary column, and it showed good thermal and physical stability, excellent chemical inertness, and unique separation properties for polycyclic aromatic compounds. These cholesteric LC copolysiloxane stationary phases show much better separation effect for the polycyclic aromatic compound than those of the nematic and smectic LC copolysiloxanes.