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Azodendrimer is a class of branched polymer, whose structure can be modulated by light irradiation. Recently, a new type of liquid crystalline dendrimers that serve as a command surface has been reported. They received tremendous attention due to the fundamental interests of the variation of their properties (e.g., alignment, topology) in response to light. Here, we explore the properties of the surface anchoring, molecular conformation and the phase structure of a model azodendrimer. We proposed a proper molecular conformation of the azodendrimer based on density functional theory analysis and molecular dynamics. Also, we reveal (1) the minimum coverage ratio of the dendrimer for inducing homeotropic alignment of host liquid crystals and the polar anchoring strength; (2) unlike typical low-molecular-weight LC molecules, different conformational states can coexist at single liquid crystalline phase; (3) the phase transition behavior of the azodendrimer is significantly affected by cooling rate because the molecular kinetics cannot follow too fast cooling.