The synthesis and characterization of side-chain liquid crystalline polysiloxanes containing (2S,3S)-4’-(2-chloro-3-methylpentanoyloxy)-4-alkanyloxybiphenyl side groups are presented. All the obtained polymers exhibit smectic mesomorphism. Those polymers containing a spacer length longer than 8 methylene units reveal respectively enantiotropic S(A), S(C)* and S(B) phases. The result demonstrates that the tendency toward the S(C)* phase increases with increasing the spacer length.