Amphiphilic, PEGylated gold nanoparticles, of approximately 2 nm average core diameter, were synthesized by reduction of hydrogen tetrachloroaurate in the presence of the ligand (1-mercaptoundec-11-yl)tetra(ethylene glycol). These PEGylated gold nanoparticles were found to assemble cleanly at the oil-water interface. This self-assembly process gave a microencapsulated oil phase, water as the continuous phase, and a monolayer of gold nanoparticles at the oil-water interface. The capsules could be cross-linked from the organic phase by reaction of the chain-end hydroxyl groups of the PEG ligands with suitable electrophiles such as terephthaloyl chloride.