Novel non-symmetric dimesogens consisting of a cholesteryl moiety and a pyrimidine unit interconnected through a pentamethylene or decamethylene spacer have been prepared through palladium-mediated Sonogashira cross-coupling. The novel mesogens show only a chiral nematic phase. The liquid crystalline phase was investigated through polarizing optical microscopy and differential scanning calorimetry. All the compounds were characterized through elemental analyses and spectral data.