A new series of thermotropic polyurethanes containing biphenyl units was synthesized by polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylene diisocyanate, with 4,4□-bis(9-hydroxynonoxy)biphenyl (BP9). Structures of the monomer and the corresponding polymers were identified using FT-IR and 1H NMR spectroscopic methods. BP9 exhibited a smectic type mesophase, however, nematic phase was found for all synthesized liquid crystalline polyurethanes except for 1,4-phenylene diisocyanate/BP9 based polyurethane. Their phase transition temperatures and thermal stability were investigated by differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray scattering. The infrared study indicated that the hydrogen bonding among urethane linkages attributed to the mesomorphism. Thermal gravimetric analysis (TGA) of synthesized polyurethanes showed that no weight loss of the polymers observed up to 280°C.