A series of well-defined rod-coil PAA-b-DPS block copolymers, containing Frechet-type dendronized polystyrene (DPS) with different generation as a rod-like hydrophobic block and poly(acrylic acid) (PAA) as a hydrophilic coil were synthesized. The procedure included the following steps: the precursor PMA-b-DPS copolymer was prepared through ATRP of Frechet-type dendritic styrene macromonomer bearing the first to the third generation (G1-G3), respectively, initiated by poly(methyl acrylate) (PMA-Br). Then, by converting PMA into PAA by subsequent hydrolysis, the targeted amphiphilic copolymers were obtained. Moreover, by using the rod-coil amphiphiles as building blocks, large compound micelles and vesicles were formed in a binary solvent mixture of DMF/H2O. Morphological changes in self-assembly showed dependence on the length of the dendronized block.