Three series of novel chiral twin liquid crystals consisting of a cholesteryl and a 4′-cyanobiphenyl-4-yloxy group (III) or a 4-cyanophenoxy group (IV) and of a dihydro-cholesteryl and a 4′-cyanobiphenyl-4-yloxy group (V) connected by an alkanoate spacer with a varying number (1–7 and 10) of methylene units were synthesized and their mesogenic properties investigated. Strong odd-even effects were observed as a function of spacer length for the phase transition temperatures, the corresponding entropy changes and the selective reflection wavelengths associated with the chiral nematic phase. The compounds with an even number of methylene units have a smaller pitch than the compounds with an odd number of methylene units. Replacement of the cholesteryl group by a dihydrocholesteryl group results in an larger pitch, whereas replacement of the 4′-cyanobiphenyl-4-yloxy group by a 4-cyanophenoxy group gives a smaller pitch.