A one-step method to synthesize a dendronized (HBP) polymers based on a polystyrene backbone with hyperbranched polyester pendant groups was described. The results show that the aromatic signals from the hyperbranched polyester occur as a series of broad peaks between 7.2 and 8.0 ppm, while those from the linear unit occur at 6.55 and 6.84 ppm. The 6:1 monomer ratio in poly(acetoxystyrene) block and hyperbranched oligomer is accounted by the loss of small oligomers during the purification process. The results show that the dendronized polymers (DHP) product do not decompose over the studied temperature range of 100-700°C. The results also show that the linear poly(4-acetoxystyrene) (PAS) is found to be readily and completely soluble in CHCl3, while the DHP and HBP is sparingly soluble.