A novel route for grafting polymers via electropolymerization of a macro-reversible addition fragmentation chain-transfer (RAFT) agent onto a conducting surface is reported. The electro-deposition of the chain transfer agent (CTA) on the conducting surface was done using cyclic voltammetry (CV). The statistically exposed dithiobenzoate moieties served as a CTA for the polymerization of styrene on a matrix of an electrodeposited conjugated polymer. The polystyrene (PS)-modified substrate was then used as the macro-CTA for the synthesis of the second block of poly-tert-butyl acrylate (PTBA) on the surface. The polymerization from the surface was characterized by surface analytical methods including AFM, XPS, and contact angle measurements. (C) 2011 Elsevier Ltd. All rights reserved.