Phase behaviour of hydrogen-bonded multicomponent mixtures of bipyridine, dodeyloxybenzoic acid and dicarboxylic acids with poly(acrylic acid) were studied at different compositions and temperatures. It was found that in certain composition ranges, the mixtures from a homogeneous liquid crystalline phase of smectic type with an unusually high enthalpy of transition into the isotropic state. The nature of the anisotropic phase observed in the polymers is discussed. The phase behaviour was studied using IR spectroscopy, differential scanning calorimetry and X-ray structure analysis.