Atom transfer radical polymerization (ATRP) catalyzed by N,N',N',N",N"-pentamethyldiethylenetriamine (PMDETA)/CuBr was performed to synthesize poly (tert-butyl acrylate) (PtBA-Br) with predesigned molecular weight and narrow polydispersity. Using the PtBA-Br as macroinitiator, the PtBA-block-PS copolymer was prepared through ATRP. After terminated bromine atom was converted to end-functional azide group (P(tBA-b-St)-N-3) C-60 end-capped PtBA-PS block copolymers (P(tBA-b-St)-C-60) were synthesized by reacting C-60 with P(tBA-b-St)-N-3. GPC characterizations showed that C-60 was chemically bonded to the end of P(tBA-b-St) chain and the products were mono-substituted. FT-IR, UV-Vis measurements confirmed that hydrolysis of P(tBA-b-St)-C-60 resulted in amphiphilic C-60 end-capped PAA-PS block copolymers. In additional, the photoconductivity of P(tBA-b-St)-C-60 was measured. (C) 2004 Elsevier B.V. All rights reserved.