The synthesis of a new coil-rod-coil ABA triblock copolymers comprised of regioregular poly(3-hexylthiopene) (P3HT) and poly(methyl methacrylate) (PMMA) segments has been demonstrated by the combination of quasi-living Grignard metathesis (GRIM) polymerization and living anionic polymerization based on 1,1-diphenylethylene (DPE) chemistry. The method involves simple reaction steps, an in situ introduction of DPE moieties at the alpha,omega-ends of P3HT and the lithiation with sec-butyl lithium (sec-BuLi) to generate a macroinitiator bearing 1,1-diphenylalkyl anions, followed by cross-over to MMA. The selective alpha,omega-ends di-functionalization is a key step to achieve the ABA structure. The structural homogeneity of the precursor and block copolymer has been confirmed by gel permeation chromatography (GPC), GPC-right angle laser light scattering (RALLS), and nuclear magnetic resonance (NMR). The block copolymer has been fully characterized by differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), Ultra-violet-visible (UV-vis) and photo luminescent (PL) spectroscopies, and atom force microscopy (AFM). (C) 2008 Elsevier Ltd. All rights reserved.