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Core-shell type star poly(methyl methacrylate) (PMMA) with benzene arborol core and linear PMMA shell having controlled chain lengths and numbers average molecular weights were synthesized by atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of multifunctional benzene arborol macroinitiator. From the point of structure of polymer, it is very important to design the monomer and polymerization for a polymer with unique structure. The obtained copolymers were characterized by GPC, 1H NMR, FT-IR, TGA and DSC. The molecular weight distributions of these copolymers were narrow (1.13 ≤ Mw/Mn ≤ 1.21). The molecular weights of core-shell star copolymer could be controlled by the molar ratios of MMA to macroinitiator for a given polymerization time. The results show that dendrimers could be used as cores to synthesize dendritic star and star-block polymers by ATRP. In addition, the polymers can self-assemble into the spherical nanoparticles in a selective solvent (DMSO/H20). [ABSTRACT FROM AUTHOR]