The electro-optical properties (tilt angle of the director and spontaneous polarisation) of eight smectic liquid crystalline compounds with a chiral centre based on (S)-(+)-3-octanol and different substitution of the benzene ring and different length of the oligomethylene spacer (−(CH2)nO−) were studied. The compounds possess the self-assembling behaviour with an antiferroelectric ordering in smectic Ca* phase at a broad temperature range, some of materials have also a ferroelectric smectic C* phase and/or an orthogonal smectic A* phase. Due to high chemical stability and very high values of the optical tilt angle (40–44°) at saturation, the tested compounds can be used as chiral components for orthoconic antiferroelectric liquid crystalline mixtures.