A series of polysiloxanes containing alkylsulfonyl side groups were synthesized using a polymer analogous reaction beginning from poly(methylhydrosiloxane) and the corresponding olefins. These polymers showed a mesomorphic behavior with smectic liquid crystalline phases. The chemical and physical properties of these polymers were examined using nuclear magnetic resonance spectroscopy, gel permeation chromatography, differential scanning calorimetry, optical polarizing microscopy, and X-ray diffraction.