A series of mesogen-jacketed liquid crystalline polymers (MJLCPs) with polysiloxane backbones have been synthesized by hydrosilylation of polymethylhydrosiloxane with styrenic derivatives Their properties were studied in detail by a combination of H-1 NMR. Fourier transform inhaled spectroscopy, differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction, scanning electron microscopy, and contact angle measurements Wide-angle X-ray diffraction results indicated that these MJLCPs based on highly flexible polysiloxane main chain could also self-assemble into supramolecular columnar nematic or smectic liquid crystalline phases compared with structurally similar MJLCPs having a polyethylene backbone, but their liquid crystalline ranges were narrowed significantly. Low contact-angle values of the MJLCPs could be attributed to the fact that the polysiloxane backbones were embedded in mesogenic side chains, which also confirmed the mesogen-jacketed model for MJLCPs