Smectic phase of formyl derivatives of azobenzene has been identified by means of polarization thermomicroscopy using a miscibility criterion. The study of dielectric properties and simulation of dipole moments and Kirkwood correlation factors have revealed that azobenzene and biphenyl derivatives containing hydroxy end group in the aliphatic terminal substituent can form supramolecules and linear associates stabilized by hydrogen bonds. The sorbents based on the studied liquid crystals have exhibited high structural selectivity with respect to isomers of various organic compounds. Thermodynamic manifestations of the specific mesogen–non-mesomorphic sorbate interactions have been revealed.