<p>In this article, we report on the liquid-crystalline properties of the 4-ω-alkenyloxy-4′-cyanobiphenyl series of compounds up to a total aliphatic chain length of eleven. When compared to the analogous fully saturated compounds, we find that the smectic layer spacing is significantly larger for the alkene-terminated materials; conversely the dielectric anisotropy in the nematic phase was found to be significantly smaller. The ability to manipulate bulk properties of nematic and smectic mesophases may have future relevance for display applications.</p