Advanced nanostructured functional materials were designed and prepared using ATRP (atom transfer radical polymerization) with ppm amounts of copper-based catalytic systems. ATRP of acrylates, methacrylates, styrenes, acrylamides, acrylonitrile and other vinyl monomers was controlled by various external stimuli, including electrical current, light, mechanical forces also in water and open air. ATRP was employed for synthesis of polymers with precisely controlled molecular architecture with designed shape, composition and functionality. Block, graft, star, hyperbranched, gradient and periodic copolymers, molecular brushes and various hybrid materials and bioconjugates were prepared with high precision. These sustainable polymers can be used as components of advanced nanostructured functional materials for applications related to environment, energy, healthcare and catalysis.