Four series of new dimers formed by interlinking chalcone and cholesterol mesogenic entities through spacers of varying length and parity have been synthesized and characterized by polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and electrical switching studies. The structure of the chalcone core has been systematically modified to investigate the effect of the molecular structure on the thermal behaviour of the dimers. The study demonstrates the dramatic dependence of thermal behaviour of these dimers on the nature of the chalcone as well as the length and parity of the spacer.