Water‐dispersible PEGylated nanoparticles (NPs) presenting amine‐reactive conjugation sites at their surfaces were synthesized and their ability to react with amines was demonstrated. An amphiphilic block copolymer bearing an N‐succinimidyl ester at its water‐soluble end was synthesized by the consecutive controlled radical polymerization of poly(ethylene glycol) methacrylate and styrene from a functional halide initiator. After purification of the copolymer, NPs of approximately 40 nm were obtained by a self‐assembly process in water. The reactivity of the NPs was evidenced by reacting them with primary amines, including a fluorescent dye. The activated ester remained stable throughout all synthetic steps and a nearly quantitative coupling efficiency was obtained.