The distribution of narrowly dispersed gold nanoparticles in hexane-in-water emulsions was studied for different surfactants. Good surfactants such as SDS and Triton X-100 block the oil-water interfaces and confine particles in the droplet. Other surfactants (Tween 85 and Span 20) form synergistic mixtures with the nanoparticles at the interfaces that lower the surface tension more than any component. Supraparticles with fully defined particle distribution form in the droplets only for surfactants that block the interface. Other surfactants promote the formation of fcc agglomerates. Nanoparticles in emulsions behave markedly different from microparticles-their structure formation is governed by free energy minimization, while microparticles are dominated by kinetics.