Oleosomes are particles equipped with a sophisticated membrane, comprising a continuous monolayer of phospholipids and hydrophobic proteins, which covers the triglyceride core and grants them extreme physical and chemical stability. The noteworthy qualities of oleosomes have attracted strong interest for their incorporation in emulsion formulations; however, little is known about their emulsifying properties and their behaviour on interfaces. For these reasons, oleosomes were isolated from sunflower seeds (96.2 wt% oil, 3.1 wt% protein) and used as an emulsifier for the stabilization of O/W and W/O interfaces. In both cases, oleosomes showed high interfacial and emulsifying activity. Individual oleosome particles had a broad size distribution from 0.4 to 10.0 μm and it was observed that the membrane of the larger oleosomes (>1-5 μm) was disrupted and its fractions participated in the newly formed interface. Oleosomes with a smaller diameter (<1 μm) seemed to have survived the applied mild emulsification step as a great number of them could be observed both in the bulk of the emulsions and on the interface of the emulsion droplets. This phenomenon was more pronounced for the W/O interface where oleosomes were absorbed intact in a manner similar to a Pickering mechanism. However, when the triglycerides were removed from the core of oleosomes in order to focus more on the effect of the membrane, the remaining material formed sub-micron spherical particles, which clearly acted as Pickering stabilisers. These findings showcase the intriguing behaviour of oleosomes upon emulsification, especially the crucial role of their membrane. The study demonstrates relevance for applications where immiscible liquid phases are present.