Poly(4-vinylphenol) was modified to poly(4-(6-(4-vinylphenoxy)hexyloxy)benzoic acid) for incorporating a flexible hexamethylene side chain with a terminal benzoic acid moiety to induce liquid crystallinity. The rigid core is generated through hydrogen bonding (H-bonding) between the pendant benzoic acid groups. The thermal stability of the modified polymer was determined by thermogravimetric analysis (TGA), whereas differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) were used to investigate the liquid crystalline behavior. The polymer exhibits mesomorphism over a wide temperature range.