Abstract: The design and synthesis of new calamitic benzothiazole-based liquid crystals, 2-[4-(4-alkyloxybenzoyloxy)phenyl]benzothiazoles, are presented. The target compound was characterized using spectroscopic techniques, such as FT-IR, NMR (¹H & ¹³C), microanalysis and EI-MS. The liquid crystalline behaviours of these compounds were thoroughly examined by differential scanning calorimetry and polarizing optical microscope techniques. These materials exhibited enantiotropic nematic phase with high thermal stability. Smectic A phase starts to emerge as monotropic phase from C10 member and changes into enantiotropic phase from C12 and persists up to C16 members.