Two kinds of acrylate monomers, i.e. 4-methoxyphenyl 4-{[2-(1-oxo-2-propenyloxy)ethyl]oxy}benzoate (I) and 4-methoxyphenyl 4-{[6-(1-oxo-2-propenyloxy)hexyl]oxy}benzoate (II) were polymerized using hyperbranched poly(p-chloromethylstyrene) (PCMS) as an initiator by atom transfer radical polymerization (ATRP). The resulting dendritic graft copolymers were characterized by means of gel permeation chromatography, differential scanning calorimetry, and polarization microscopy. The mesophase behaviour of these dendritic copolymers essentially depends on the chemical nature of the polyacrylates.