Four series of thermotropic polyurethane elastomers (TPUEs) were synthesized in this study. The hard segments were formed by using 4,4’-methylenedicyclohexyl diisocyanate (H(12)MDI) reacted with various mesogenic units, such as benzene-1,4-di(4-iminophenoxy-n-hexanol), benzene-1,4-di(4-iminophenol), and 3,3’-(4,4’-biphenylene)dipropanol, which also acted as the chain extender. Poly(oxytetramethylene)glycols (PTMEGs), PTMEG-2000 (M(n) 2,000) and PTMEG-1000 (M(n) 1,000) were used as a soft segment. The structures of all synthesized thermotropic liquid crystalline polyurethanes (TLCPUs) were characterized by FTIR spectroscopy. The effects of mesogenic units on the LC properties and elastic behaviors of LCPUs were studied. It was difficult to show LC behaviors for the PU elastomers derived from the mesogenic units with a lower aspect ratio, such as 3,3’-(4,4’-biphenylene)dipropanol, or the long soft segments, PTMEG-2000. In addition, these PU elastomers show better elastic properties by using a higher aspect ratio mesogenic unit as the chain extender, such as benzene-1,4-di(4-iminophenoxy-n-hexanol and benzene-1,4-di(4-imino-phenol). The thermal properties were investigated by DSC measurements, thermal optical polarized microscopy, wide angle X-ray diffraction, dynamic mechanical analysis, and thermogravimetric analysis. The mechanical properties mere measured by a tensilemeter.