Abstract Homopolymers of poly[ N ‐(2‐(diethylamino)ethyl) acrylamide] exhibit the ability to adsorb onto the surface of preformed or growing gold nanoparticles. The resulting hybrid materials possess a pH and thermo‐sensitive nature. Consequently, their optical properties can be modulated by manipulating either the temperature or the pH. Moreover, introducing monomers based on poly( N ‐isopropyl acrylamide) into block or random statistical polymers enables further modulation of the thermosensitive properties. These copolymers, employed for the in‐situ synthesis and/or stabilization of gold nanoparticles, lead to hybrid materials whose properties and/or particle size depend on the polymer composition and microstructure: statistical polymers emerge as superior stabilizing agents compared to their block counterparts at a constant composition.