Herein, a novel strategy to overcome the influence of π−π stacking on the rod-coil copolymer organization of is reported. A diblock copolymer poly(3-hexylthiophene)-block-poly(ethylene glycol methylether methacrylate) P3HT-b-PEGMA was synthesized by a Huisgen cyclo-addition, so-called "Click chemistry", combining the P3HT and PEGMA blocks synthesized by Atom Transfer Radical Polymerization (ATRP) and Kumada Catalyst Transfer Polymerization (KCTP), respectively. Using a dip-coating process, the original film organization of the diblock copolymer was controlled by the crystallization of the P3HT block via π−π stacking. The morphology of the P3HT-b-PEGMA films was influenced by the incorporation of gold nanoparticles GNPs coated by Poly(EthyleneGlycol) ligands. Indeed, the crystalline structuration of the P3HT sequence was counterbalanced by the addition in the film of gold nanoparticles finely localized within the copolymer PEGMA matrix. Transmission Electron Microscopy (TEM) and ToF-SIMS analysis validated the GNPs homogeneous localization into the compatible PEGMA phase. Differential Scanning Calorimetry (DSC) showed the rod block crystallization disruption. A morphological transition of the self-assembly is observed by Atomic Force Microscopy (AFM) from P3HT fibrils into out of plane cylinders-like driven by the nanophase segregation. 2