Tailoring of High‐Order Multiple Emulsions by the Liquid–Liquid Phase Separation of Ternary Mixtures

Multiple emulsions with an “onion” topology are useful vehicles for drug delivery, biochemical assays, and templating materials. They can be assembled by ternary liquid phase separation by microfluidics, but the control over their design is limited because the mechanism for their creation is unknown. Herein we show that phase separation occurs through self‐similar cycles of mass transfer, spinodal decomposition or nucleation, and coalescence into multiple layers. Mapping out the phase diagram shows a linear relationship between the diameters of concentric layers, the slope of which depends on the initial ternary composition and the molecular weight of the surfactant. These general rules quantitatively predict the number of droplet layers (multiplicity), which we used to devise self‐assembly routes for polymer capsules and liposomes. Moreover, we extended the technique to the assembly of lipid‐stabilized droplets with ordered internal structures.