The synthesis and characterization of monodisperse ferroelectric side chain liquid-crystalline siloxane oligomers (from monomer to pentamer) having a mesogenic group consisting of (S)-(-)-4-(((2-methylbutyl)oxy)carbonyl)phenyl 4’-(octyloxy)biphenyl-4-carboxylate are described. The controlled hydrolysis of dichloromethylsilane with water resulted in a mixture of alpha,omega-dichloro-alpha,omega-dimethylsiloxane oligomers. These were then fractionated by distillation and end-capped with trimethylsilanol sodium salt. The products were purified by distillation and characterized by gas chromatography/mass spectroscopy (GC/MS) analysis. The hydrosilylation of the methylsiloxane oligomers with the vinyl mesogen was carried out in the presence of platinum divinyltetramethylsiloxane catalyst. The products were purified by column chromatography. The liquid-crystalline properties of the oligomers were confirmed by differential scanning calorimetry (DSC), optical polarized microscopy (OPM), and electrooptical-measurement. All the oligomers displayed S-A and S-C(*) mesophases. A very steep increase of transition temperatures (clearing as well as S-A-S-C(*) transition) was observed until the trimer, and then the increase became less steep as the degree of polymerization increased. The d-spacing of the oligomers in the S-A phase, determined by X-ray diffraction studies, agreed with the length of the repeat unit which was calculated by molecular simulation. This suggested that the S-A phase had a monolayer structure. The tilt angle of the S-C(*) phase reached saturation at about 20 degrees C below the S-A-S-C(*) transition point (T-c varied in the order monomer < trimer < dimer < pentamer < tetramer, revealing an odd-even effect, wherein the largest P-s value of 90 nC/cm(2) was observed for the tetramer.