The synthesis of side-chain liquid crystalline copolysiloxanes containing ω-[4-[4-[(S-2-methylbutoxy]phenoxycarbonyl]-2-chlorophenoxy]alkyl side groups is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffractometry reveal smectic mesomorphism for most of the obtained polymers. The copolysiloxane with three methylene units in the spacer is the only one showing no mesomorphic property. The other four copolysiloxanes, containing four, five, six or eleven methylene units in the spacer, display a smectic A phase. All of the obtained polymers present dual glass transition behavior by both DSC and thermally stimulated current (TSC) techniques. The first glass transition (Tg1) at lower temperature is due to the segmental motions of the polysiloxane backbone, while the second glass transition (Tg2) is due to the cooperative relaxation motions of spacers and mesogenic units.