We describe a series of well-defined dendritic-linear block copolymer architectures via the reversible addition-fragmentation chain transfer (RAFT) polymerization technique. Using dendritic chain transfer agents (CTA)s possessing a single dithioester moiety at the focal point, RAFT polymerization was carried Out to attach polystyrene (PS) and poly(methyl methacrylate) (PMMA) chains of controlled lengths by kinetic control. To provide electrochemical functionality, the dendritic CTAs were designed with carbazole moieties at the periphery of the structures. The results on the electrochemical polymerization of the carbazole moieties at the periphery of the dendritic component of the block copolymers reveal quantitative cyclic depositions with changes in viscoelastic properties of the deposited films as monitored by the electrochemical quartz crystal rnicrobalance technique. The electroactive dendritic blocks proved to be an effective electrochemically active macromonomer for the electrodeposition of these structures on conducting substrates.