We have investigated the effect of particle shape in Pickering emulsions by employing, for the first time, cubic and peanut-shaped particles. The interfacial packing and orientation of anisotropic microparticles are revealed at the single-particle level by direct microscopy observations. The uniform anisotropic hematite microparticles adsorb irreversibly at the oil–water interface in monolayers and form solid-stabilized o/w emulsions via the process of limited coalescence. Emulsions were stable against further coalescence for at least 1 year. We found that cubes assembled at the interface in monolayers with a packing intermediate between hexagonal and cubic and average packing densities of up to 90%. Local domains displayed densities even higher than theoretically achievable for spheres. Cubes exclusively orient parallel with one of their flat sides at the oil–water interface, whereas peanuts preferentially attach parallel with their long side. Those peanut-shaped microparticles assemble in locally ordered, interfacial particle stacks that may interlock. Indications for long-range capillary interactions were not found, and we hypothesize that this is related to the observed stable orientations of cubes and peanuts that marginalize deformations of the interface
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