Atom transfer radical polymerizations (ATRPs) of 1-(4-methaeryloyloxybenzyl)thymine (MAT) and 9-(2-methacryloyloxyethyl)adenine (MAA) were conducted for the synthesis of DNA-base functionalized polymers. The association equilibrium constant K-asso between MAT and MAA and the complexation equilibrium constant K-comp between the corresponding polymers PMAT and PMAA were determined. A zipper-like diblock copolymer, PMAT-b-PMAA, was prepared by anchoring the PMAT and PMAA blocks on the ortho-positions of a pyridine ring via a successive two-step ATRP. Dynamic light scattering and atom force microscopy confirmed that the block copolymer had a V-shaped configuration in dimethylsulfoxide/N,N-dimethylformamide. (c) 2006 Wiley Periodicals, lnc.