Poly(propyleneimine)-based liquid crystalline dendrimers (DCDs) with a relatively flexible dendritic scaffold were successfully prepared by Michael addition reaction of polypropyleneimine)s to 6-(2,3-dicyano-4-butoxyphenyloxy) hexyl acrylate(4). The structure of DCDs were characterized by IR, NMR and MALDI-TOF mass spectroscopies. Liquid crystallinity were examined by DSC, polarized optical microscope, and X-ray diffraction methods. DCDs exhibited a smectic liquid-crystalline phase, The polar terminal 2,3-dicyanophenylene group gave a liquid crystalline properties to DCDs.