Aggregation of gold nanoparticles into soluble spherical assemblies using bi-functional ligands i.e., dithiols has recently been demonstrated but with limited control over the size of such assemblies. Herein, we report a new approach to further control the size of water dispersible spherical assemblies by confining gold nanoparticles in tiny oil droplets in water (oil-in-water emulsions) followed by their cross-linking with alkanedithiols. By controlling the size of the oil droplets and the concentration of nanoparticles, the size of spherical aggregates can be controlled from 20 to 400 nm. Cryo-TEM micrographs confirm the formation of covalently-linked soluble spherical nanoparticle assemblies within the oil emulsions in water. Such size-controlled nanoparticle assemblies may have several potential applications including those in gas sensors, controlled delivery, and optical coatings. (C) 2010 Elsevier Inc. All rights reserved.