A series of new organosiloxane ferroelectric liquid crystalline (FLC) materials have been synthesized, and their mesomorphic and physical properties have been characterized. Four new disiloxanes and trisiloxanes, containing biphenyl 4-hydroxybenzoate and phenyl 4-hydroxybiphenylcarboxylate as mesogenic units and eleven methylene unit as spacers and (2S,3S)-2-chloro-3-methylvalerate unit as chiral end groups. The molecule, using three phenyl ring as a mesogenic unit, formulates much wider liquid crystalline phase temperature ranges than that of a two phenyl ring unit. The phenyl arrangement differences of mesogenic unit result in the greater differences of the liquid crystal phase formation. The siloxane molecule induction is helpful to the more regular smectic phase formation and smectic phase stabilization, such as chiral S-C (S-C*) and S-B phases. The siloxane molecule is helpful to reduce the phase transition temperature and broaden the liquid crystal temperature range of the S-C* phase and, simultaneously, it will not induce chain crystallization phenomenon and dilute the Ps value. The synthesis and characterization of the new FLCs materials, which exhibit a room temperature S-C* phase and higher spontaneous polarization are presented.