Hypothesis: Multiphase droplets form when oil and water are mixed together at the ambivalent conditions that occur close to phase inversion. In this paper we propose a mechanism for the stabilisation of multiphase droplets by a single population of particles. Experiments: We investigated the microstructure of emulsions formed when dodecane and water are mixed in the presence of hydrophobic fumed silica nanoparticles. We identified the range of compositions, mixing times and rates where water-in-oil-in-water emulsions are stabilised in a single mixing step. To explore how the particle availability and mixing conditions lead to multiple emulsion formation we used light scattering and microscopy techniques to probe the size and morphology of the drops, and the particle coverage of the interfaces. Findings: Our key finding is that to stabilise multiphase drops there should be sufficient particles available to coat water drops that are entrained within coalescing oil droplets. The size of an entrained drop is determined by the volume of the rupturing film that forms between the oil drops. The particle coating prevents the entrained drop from escaping into the external aqueous phase. These results suggest a simple route for controlling the formation and stability of multiple emulsions for encapsulation applications. (C) 2019 Elsevier Inc. All rights reserved.