Well-defined polystyrene- (PSO or poly(epsilon-caprolactone) (PCL)-based polymers containing mid- or end-chain 2,5 or 3,5-dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). 1,4-Dibromo-2-(bromomethyl)benzene, 1,3-dibromo-5-(bromomethyl)benzene, and 1,4-dibromo-2,5-di(bromomethyl)benzene were used as initiators in ATRP of styrene (SO in conjunction with CuBr/2,2'-bipyridine as catalyst. 2,5-Dibromo-1,4-(dihydroxymethyl)benzene initiated the ROP of epsilon-caprolactone (CL) in the presence of stannous octoate (Sn(Oct)(2)) catalyst. The reaction of these polymers with amino- or aldehyde-functionalized monoboronic acids, in Suzuki-type couplings, afforded the corresponding telechelies. Further functionalization with oxidable groups such as 2-pyrrolyl or 1-naphthyl was attained by condensation reactions of the amino or aldehyde groups with low molecular weight aldehydes or amines, respectively, with the formation of azomethine linkages. Preliminary attempts for the synthesis of fully conjugated poly(Schiff base) with polymeric segments as substituents, by oxidative polymerization of the macromonomers, are presented. All the starting, intermediate, or final polymers were structurally analyzed by spectral methods (H-1 NMR, C-13 NMR, and IR). (c) 2005 Wiley Periodicals, Inc.