Dynamic Assembly of Microgels and Polymers at Non‐Aqueous Liquid/Liquid Interfaces

Abstract Particle assembly at liquid–liquid interfaces presents a promising bottom‐up strategy for creating supramolecular materials with advanced functionalities. However, the significantly lower interfacial tension observed in immiscible organic phases compared to traditional oil–water systems has hindered the effective adsorption and assembly of particles at oil–oil interfaces. In this work, a versatile and effective strategy is presented that utilizes the assembly and jamming of microgels and polymer ligands at non‐aqueous liquid–liquid interfaces to create non‐aqueous Pickering emulsions and reconfigurable droplet networks. The resulting microgel‐polymer complexes form an asymmetric interfacial bilayer with high surface coverage, which effectively minimizes interfacial energy and improves interfacial elasticity. Through a combination of systematic interfacial measurements and molecular dynamics simulations, the underlying mechanisms governing interfacial self‐assembly are elucidated. Notably, the stimuli‐responsive nature of the microgel‐polymer complexes allows for precise control over the interfacial assembly and disassembly by introducing competitive molecules. Furthermore, it is demonstrated that these non‐aqueous Pickering emulsions serve as excellent templates for the fabrication of heterogeneous organogels and microgel‐based colloidosomes through both covalent and non‐covalent crosslinking strategies. This work underscores the potential of non‐aqueous interfaces in advancing materials science and opens new avenues for developing multifunctional materials.