Poly(4-vinylphenol) was modified to poly(4-(4-vinylphenoxy)butan-1-ol) and poly(4-(6-(4-vinylphenoxy)hexyloxy)benzoic acid). Methyl 4-((E)-2-pyridin-4-yl)vinyl)benzoate ligand was synthesized and hydrogen bonded with two modified polymers. Complexes of poly(4-vinylpyridine) with another series of ligands, 6-hydroxyhexyl 4-(E)-4-alkoxy)styry)benzoates, have also been prepared. The liquid crystalline properties of the blends have been investigated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Complexes of methyl 4-((E)-2-pyridin-4-yl)vinyl)benzoate with the two modified polymers show grainy texture of nematic phase, whereas the complexes of poly(4-vinylpyridine) with styrylbenzoate ligands exhibit smectic phases.