In this study, a strategy was developed for the synthesis of nano-sized, silica-ceria, core-shell composites in a water-oil (W/O) microemulsion consisting of water, heptane and the binary surfactants AOT (sulfosuccinic acid bis (2-ethylhexyl) ester sodium salt) and NP-5 (polyoxyethylene (5) nonylphenyl ether). The core-shell, silica-ceria particles were prepared in a stepwise procedure: (1) the precipitation of the core-silica particles in a W/O microemulsion and (2) the surface precipitation of ceria on the core silica dispersed over the microemulsion. The composition of the binary surfactant greatly influenced the growth rate of the core-silica particles. The virial coefficient of diffusion was utilized to estimate the effect of the surfactant composition on the degree of intermicellar interaction that is important for the growth rate of the silica along with the flexibility of the micellar interface and the structure of the water domain. The deposition of the ceria on the core silica was not straightforward because the bulk and surface precipitation competed with each other. The promotion of surface precipitation was attempted by: (1) chemically modifying the silica surface with an organoamine group and (2) slowing down the precipitation rate of the ceria in a semi-batch operation. These attempts successfully produced the nano-sized silica-ceria, core-shell particles, which were evidenced through the TEM, XPS and zeta potential analysis. (C) 2010 Elsevier Inc. All rights reserved.