The synthesis of five chiral liquid crystalline monomers (M 1 –M 5 ), and their corresponding side-chain polymers (P 1 –P 5 ) based on (S)-(+)-2-methyl-1-butanol derivatives is described. The chemical structures of the monomers were confirmed by FT-IR, 1 H NMR, and elemental analyses. The structure-property relationships of the monomers and polymers obtained are discussed. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. All monomers showed a cholesteric phase. For M 2 , M 3 , and M 5 , besides a cholesteric phase and a smectic A (S A ) phase, M 2 also revealed an enantiotropic chiral smectic C (SC∗) phase and a monotropic smectic B (S B ) phase, and M 3 also showed a S B phase. The polymers P 1 –P 5 exhibited a S A phase, moreover, P 2 , P 3 and P 5 also revealed a SC∗ phase. The experimental results demonstrated that a flexible siloxane backbone and a long flexible spacer tended to exhibit a low glass transition temperature, high thermal stability, and wide mesophase temperature range.