Two kinds of dendronized polymers [poly((4-3,4,5)-12G1-CH(2)MA) and poly(G2-CH(2)MA)] were synthesized successfully by atom transfer radical polymerization (ATRP). The polymerization carried out with CuBr/ N,N,N',N',N'-pentamethyldiethylenetriamine (PMDETA) as catalyst/ligand system led to the polymers with narrow polydispersity (1.14 < M-omega/M-n < 1.35). The dendronized polymers obtained with retained reactivity at chain end were further utilized as macroinitiators to the chain extensive reaction of a second monomer (St) by ATRP, which resulted in the formation of a new type of linear-dendritic diblock copolymers. In addition, the polymers and their diblock copolymers were characterized by GPC and DSC. (C) 2003 Wiley Periodicals, Inc.