A novel liquid crystalline dendrimer with peripheral mesogenic units was successfully prepared. Azo-reaction and Williamson synthesis were employed in the preparation of the mesogenic unit 4-[4-(6-hydroxyhexyloxy)-phenylazo]nitrobenzene (M-NO2). A terminal Si—Cl functional carbosilane dendrimer based on pentaerythritol was used as dendritic scaffold and subsequently functionalized with the aforementioned groups. Investigation of the liq-uid crystalline properties of the mesogen-functionalized dendrimer PCSi-1G-NO2 by polarizing optical microscopy, DSC, and X-ray diffraction showed that it exhibits smectic E (SE) phase, different from the corresponding mesog-enic unit, which shows nematic phase. Furthermore, the temperatures of both the melting point and the clearing point of the mesogen-functionalized dendrimer decrease, and the temperature region of the SE phase is wider than that of the nematic phase. A novel liquid crystalline dendrimer with peripheral mesogenic units was successfully prepared. Azo-reaction and Williamson synthesis were employed in the preparation of the mesogenic unit 4- [4- (6-hydroxyhexyloxy) -phenylazo] nitrobenzene (M-NO2). A terminal Si-Cl functional carbosilane dendrimer based on pentaerythritol was used as dendritic scaffold and subsequently functionalized with the groups groups. Investigation of the liq-uid crystalline properties of the mesogen-functionalized dendrimer PCSi-1G-NO2 by polarizing optical microscopy, DSC, and X -ray diffraction showed that it exhibits smectic E (SE) phase, different from the corresponding mesog-enic unit, which shows nematic phase. Furthermore, the temperatures of both the melting point and the clearing point of the mesogen-functionalized dendrimer decrease, and the temperature region of the SE phase is wider than that of the nematic phase.