The first- and second-generation dendronized polymers, poly (2, 5-bis {[3, 5-di (4 '-methoxy-4-oxyhexyloxy azobenzene) benzyl] oxycarbonyl} styrene) (PG1) and poly (2, 5-bis {3, 5-di [3, 5-di (4 '-methoxy-4-oxyhexyloxy azobenzene) benzyl] oxycarbonyl} styrene) (PG2), were successfully synthesized, and their phase structures were investigated by differential scanning calorimetry (DSC), polarized light microscopy (PLM), and one-dimensional wide-angle X-ray diffraction (1D WAXD). The results show that the liquid crystalline (LC) phase structures of the dendronized polymers containing dendritic azobenzene side groups depend strongly on the molecular weights (MWs) and the generation of dendritic azobenzene side groups. Compared the low MWs PG2 with the low MWs PG1, the degree of order in LC phase increased with increasing the generation of dendritic azobenzene side groups.