Liquid crystalline of a new carbosilane dendrimer of the second generation(D2) containing thirty-six 4-nitroazobenzene groups in its periphery was characterized by means of polarizing optical micrograph, DSC and WAXD. Mesogenic compound M5 exhibits threaded, schlieren and inversion lines texture of the nematic phase on the cooling from isotropic phase to solidified temperature. Dendrimer D2 shows the focal conic fan-shaped texture of the smectic A phase on the heating course from 69 to 187 ℃ and on the cooling course from 183 to 64 ℃. After cooling, the smectic E(S E) phase with a texture of the focal conic fan-shape with stripes and concentric arcs appears from smectic A(S A) phase. Phase behavior of dendrimer D2 in liquid crystalline state was K69S A187I182S A57S E47K. The isotropic-smectic A transition enthalpy, smectic A-smectic E transition enthalpy and isotropic-smectic A transition entropy were 1.8, 4.5 and 4.0 J/(K·mol), respectively, and were in agreement with or close to those of small molecular liquid crystal.