The mechanical and thermal properties, in particular the shape memory effect, of TPUs synthesized from diol-terminated poly(caprolactone) (PCL diol), 4,4＇-diphenylmethane diisocyanate (MDI), and mesogenic chain extenders, 4,4＇-bis-(2-hydroxyethoxy)biphenyl (BEBP) or 4,4＇-bis-(6-hydroxyhexoxy)biphenyl (BHBP) were examined and compared with results for PCL diol/MDI/1,4-butanediol (BD) based TPUs in a previous study. Some results related to the rigid structure of BEBP or BHBP were observed in the thermomechanical properties. Shape fixity was related to the crystallization of the PCL phase.