A series of new cholesteric liquid-crystalline polysiloxanes derived from steroid substituents were synthesized. The chemical structures of the monomers or polymers obtained were characterized by FTIR, element analyses, H-1 NMR, and C-13 NMR. Their mesogenic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. Monomers exhibited typical cholesteric focal-conic or spiral texture. The polymers P-1-P-6 showed cholesteric phase and P, displayed smectic phase. (c) 2005 Wiley Periodicals, Inc. J Appl Polyrn Sci 99: 2330-2336, 2006