Important parameters of hydroxybutyl 4-aroyloxybenzoate ligands were calculated and correlations were made between theoretical and experimental results. In addition, supramolecular side-chain liquid crystalline polymers of the ligands with poly(4-vinylpyridine) were synthesized. Hydrogen bond formation was ascertained by Fourier tranform infra-red spectroscopy. The stabilities of the complexes were determined by thermogravimetric analysis. The mesomorphic behaviorwas investigated using differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction analysis. Semiempirical study revealed that a ratio of similar to 1.2 in the lengths of flexible and rigid parts of the molecules is the most favorable for a wider liquid crystal (LC) temperature range.