Herein, we report how functional gold nanoparticles can drive the block copolymer BCP thin film morphologies of polystyrene-block-poly(vinylbenzyl-3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)prop-1-yne (PS-b-PVBEG). PS-b-PVBEG was obtained via Nitroxide Mediated Polymerization and two consecutive post-polymerization modifications, a nucleophilic substitution (SN2) between polystyrene-b-poly(vinylbenzyl chloride) (PS-b-PVBC) and NaN3, and a Huisgen cycloaddition with mPEG3-propargyl. The self-assembly in bulk of the intermediate block copolymers PS-b-PVBC and PS-b-PVBN3 and the final PS-b-PVBEG one were studied as well as the change of the morphology of PS-b-PVBEG with the incorporation of polystyrene-capped gold nanoparticles (GNPs@PS). The morphology of the hybrid films was characterized by Atomic Force Microscopy (AFM) and the correlation between the morphology and the chemical composition of the surface is finely investigated by X-ray Photo-electron Spectroscopy (XPS). A high correlation is observed between the chemical composition of the surface of the hybrid film and its morphology transition from PS lamellae to out-of-plane PVBEG cylinders by GNPs@PS addition.