Abstract: The liquid crystalline monomers: M1 (4-allyloxy-phentylpropionyloxycholesterol ester) and M2 (4-undecanoyloxy-4-cyanogen-biphenyl ester) were synthesized. Then, a series of chiral liquid crystalline polymers containing electron withdrawing groups were prepared via graft copolymerization with the dosages of M1, M2 and PMHS(polymethylhydrosiloxane) as backbone in a certain proportion. The chemical structures of both the monomers and polymers thus obtained were confirmed by FT-IR and ¹H NMR spectra, and the mesomorphic properties were investigated by DSC, POM, TG and X-ray. Experiment results showed that M1 and M2 are cholesteric and nematic liquid crystal monomers, respectively, and polymer P1 smectic but P2~P8 are chiral smectic A polymers. Furthermore, the glass transition and clearing points of the polymers tend to increase with the increasing content of M1, with a wide range of liquid crystalline phase provided.