A series of biodegradable segmented liquid crystalline poly(ester-urethane)s were prepared by solution polymerization of poly(L-lactic acid) (PLLA), mesogenic diol prepolymer poly(butylene terephthaloyldioxy dibenzoates) (MD), and hexamethylene diisocyanate (HDI). The MD content was varied from 0 to 40 mol% so that the effects of the mesogen content on the thermal and physical properties, and hydrolytic degradation were examined respectively. It was found that introducing mesogens units could increase the thermal stability and the elastic properties, while reduced the phase transition temperatures and the hydrolytic degradation rate.