A fast and simple bottom-up methodology is reported to allow, thanks to a spontaneous phenomenon, the grafting of various materials on polymer substrates. In 60 s, the inert surface of polystyrene material is converted into a functional platform onto which organic molecules and metal particles can be anchored. A polystyrene (PS) matrix is blended with a small amount of a diblock copolymer additive engineered to both segregate at the material surface and be able to involve chemical reaction. Indeed, poly(pentafluorostyrene) (PSF) contains surface active fluorine atoms and the nucleophuge para-fluorine atom that allows nucleophilic substitution with thiols. Films of blend of PS matrix and PS-b-PSF additive are submitted to a microwave annealing to accelerate the spontaneous surface segregation of fluorine low surface energy atoms. XPS was performed to find that the optimal annealing conditions was a treatment at 30 W during 60 s. With this procedure, a blend of 5 w% in additive can lead to a surface composed of 13 at% of fluorine atoms corresponding to 55 w% of diblock. The pentafluorostyrene units decorating the surface were used as anchors to immobilize gold nanoparticles via the para-fluoro-thiol click reaction.