Two new series of hydrogen bonding liquid crystal dimers were prepared and their selfassemble behavior and structure-property relationships were studied through intermolecular hydrogen bond formation. The first series of symmetric liquid crystal dimers have two terminal alkoxy chains and the second have four terminal alkoxy chains. Their structures were elucidated using spectroscopic techniques, elemental analysis, and powdered X-ray diffraction. The mesophases and their corresponding transition temperatures were identified by differential scanning calorimetric measurements and polarized optical microscope.