AbstractA new class of mesogenic α,ω‐alkylene bis[4‐(4‐acryloyloxybenzoyloxy)benzoate]s1a — 1gwere synthesized and studied for their mesophase behaviour. The thermodynamic parameters of the isotropization transitionTi, ΔHiand ΔSishow distinct odd‐even alternations and demonstrate that the thermotropic liquid crystalline properties in homologous series of mesogens can not be a continuous function of the length of the inner spacer segment. It is anticipated that the investigated diacrylates are of value as precursors of thermotropic semiflexible polymers, crosslinking agents for mesomorphic polymer networks and low molecular weight twin mo