Diblock copolymers comprising a highly biocompatible poly(2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC) block and a poly(2-(dimethylamino) ethyl methacrylate) (PDMA) block were evaluated for the synthesis of sterically stabilized gold nanoparticles in aqueous solution. The PDMA block becomes partially protonated on addition of HAuCl4, and the remaining nonprotonated tertiary amine groups reduce the AuCl4- counterion to zerovalent gold in situ. This approach results in the adsorption of the PDMA block onto the gold nanoparticle surface while the PMPC chains serve as a stabilizing block, producing highly biocompatible gold sols in aqueous solution at ambient temperature without any external reducing agent. The size and shape of gold nanoparticles could be readily controlled by tuning synthesis parameters such as the block composition and the relative and absolute concentrations of the PMPC-PDMA diblock copolymer and HAuCl4. These highly biocompatible gold sols have potential biomedical applications.