New series of chiral thiols with three aromatic rings and the N = N group in the molecular core have been synthesized and grafted on polybutadiene diols backbone. The resulting polymers possess the OH end groups for possible preparation of the liquid crystal ordered networks. Basic properties of the thiols and resulting polybutadiene diols have been studied by polarizing microscopy and differential scanning calorimetry. The resulting diol-based polymers show the liquid crystalline behaviour in a broad temperature range. The effect of the side chain structure and density of grafting on the properties of polybutadiene diols has been studied and discussed.