The synthesis and characterization of 1-(4-hydroxyphenyl)-2-(4-hydroxy-4’-biph (TPB’) which is the constitutional isomer of 1-(4-hydroxy-4’-biphenylyl)-2-(4-hydroxy (TPB) and of the corresponding polyethers with alpha,omega-dibromoallcanes (TPB’-X with X = 4-19, where X = number of methylenic groups in the spacer) are described. The phase behaviour of TPB’-X is similar to that of TPB-X previously reported from our laboratory (Macromolecules 1991, 24, 6318), except that both the crystalline melting and the nematic-isotropic temperatures of TPB’-X are higher than those of TPB-X. Since the increase of the isotropization temperature is larger than that of the melting temperature, at long spacers virtual mesophases of TPB-X became monotropic for TPB’-X. This is explained by the difference between the axial ratio (x = L/d) of these two constitutional isomers, i.e., x = 1.46 for TPB and x = 2.01 for TPB’. TPB-X and TPB’-X are isomorphic within their nematic and crystalline phases.