We demonstrate the electrostatic assembly of oppositely charged silica particles into an ensemble of well-defined core-satellite supraparticles, which are a type of patchy particle. To achieve controlled heteroaggregation, we used oppositely charged silica particles with different sizes ranging from 5 nm to 150 nm at several concentrations. The assembly works best with larger particles, resulting in a fairly low polydispersity and a low amount of bridging between the individual clusters. Using smaller particles produces high polydispersity, large clusters and uncontrolled aggregation and bridging. Furthermore, even with controlled aggregation into well-defined clusters in the case of bigger particles, we observe an uneven covering of the central particles with around 1-6 satellite particles adsorbed to the central particle. This behavior is not predicted by simple pairwise DLVO potentials which would anticipate an even spacing of the satellite particles on the core. We explain these observations by taking into account the interactions of the adsorbing particles within the ionic cloud of the central particle. We hypothesize that when the adsorbing satellite particles are small compared to the diameter of the ion cloud of the core particle, they aggregate within the ion cloud and therefore do not create a well-defined monolayer on the surface of the core particle, instead forming small agglomerates during adsorption. Finally, both the assembled zwitterionic clusters and clusters that were partially hydrophobized were tested for their capabilities as Pickering emulsifiers. The zwitterionic clusters showed a strongly increased surface activity compared to the individual particles, while the hydrophobized particles changed the emulsion type from w/o to o/w. Interfacial dilatational rheological tests supported the observations from the emulsion tests. With this, we demonstrate that a relatively unordered ensemble of supraparticles is able to show well-defined functionality at a higher hierarchical level as Pickering emulsifiers. (C) 2017 Elsevier Inc. All rights reserved.