A thermotropic liquid crystalline polyurethane (LCPU) was synthesized by the polyaddition reaction of 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI) with 4,4-bis(6-hydroxyhexoxy)biphenyl (BHHBP). The liquid crystalline behavior of the polymer was investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide angle X-ray diffraction (WAXD). The LCPU exhibited a nematic phase with a threaded texture and had a wide mesophase temperature range. And thermogravimetric analysis (TGA) indicated the decomposition temperature of the LCPU was >300°C. The observation of POM showed that the LCPU was a thermotropic nematic liquid crystalline polymer at certain temperature range.