We describe a facile protocol for the synthesis of PEGylated Au nanoparticles by simply mixing aqueous solutions of HAuCl4 and oligo(ethylene glycol) ethyl ether methacrylate. This method was applied to generate uniform multiply-twinned Au nanostructures of ∼21 nm in diameter with high yields. Our proposed mechanism indicates that the generation of primary alcohol intermediates from the nucleophilic addition reaction of water (nucleophile) with AuIII–vinyl complex is responsible for the reduction of gold ions. This protocol was also used to synthesize Ag nanoparticles and small aggregates of Pd nanoparticles. Due to the exclusion of sophisticated synthesis of PEG containing stabilizers, additional surfactants, or reducing agents, this approach provides a remarkably simple, versatile, and environmentally benign protocol to prepare PEGylated noble-metal nanocrystals. A comparative BSA adsorption study proved the lack of non-specific binding, a common obstacle in designing biocompatible nanoparticles.