Herein, we report the functionalization of selective nano-domains driven by the self-assembly of a polystyrene-block-poly(vinyl benzyl azide) PS-b-PVBN3 copolymer synthesized in three steps. First, a Polystyrene macro-initiator was synthesized, and then extended with vinyl benzyl chloride by Nitroxide Mediated Polymerization to form a polystyrene-block-poly(vinyl benzyl chloride) PS-b-PVBC. Nucleophilic substitution of the chloride into an azide moiety is then performed to obtain the PS-b-PVBN which self-assembled to form cylindrical domains of polystyrene and vinyl benzyl azide. Click chemistry was then used to chemically bind functional gold nanoparticles and poly(N-isopropylacrylamide) (PNIPAM) on PVBN3 domains due to the specific anchor at the surface of the nanopatterned film. Atomic Force Microscopy (AFM) was used to observe the block copolymer self-assembly and gold nanoparticles alignment at the surface of the PVBN3 nanodomains. Thorough X-ray Photoelectron Spectroscopy (XPS) analysis of the functional film showed the evidence of the sequential grafting of nanoparticles and PNIPAM. The hybrid surface expressed thermoresponsive properties and serve as pattern to perfectly align and control the assembly of inorganic particles at the nanoscale. 2