synthetic ways, generating a diverse range of multicompartment assemblies. [4,5] Analogous to cellular tissues, multicompartment assemblies on micro or macro scales can be designed with complex morphologies and multiple functions by rationally organizing building blocks, finding wide applications in artificial cells, [6] cascade reactions, [7] responsive materials, [8] signal communication, [9] and therapeutic applications. [10] For the preparation of multicompartment assemblies, bottomup assembly from building blocks is most widely adopted as this approach enables precise and independent control over individual chambers, where the physical and chemical characteristics of multicompartment architectures can be dictated. For example, exploiting surface tension and hydrophobic interactions at the liquidgas interface, A. Khademhosseini and coworkers completed the ordered assembly of cell-loaded hydrogels and obtained biotissue-like structures. [11] S. Chen's group prepared hydrogel microspheres as building blocks by microfluidics and successfully constructed multicompartment ensembles at multidimensional scales through hydrogen bonding and host-guest interactions between microspheres. [12] In another work, they first prepared a Janus microsphere, which was then partially fused with a certain number of other microspheres regulated by a magnetic field. In this way, they fabricated molecule-analog photonic crystal structures. [13] Besides, through introducing dynamic covalent bonding between amino and carbonyl compounds, B. Tang and his co-workers generated magic cube-like assemblies from aggregation-induced fluorescence molecule (AIE) doped hydrogel and studied their luminescence and deformation properties. [14] Although many advances made, there are some limitations within bottom-up processes towards multicompartment assemblies. Above all, the realization of assemblies generally requires elaborately designed building blocks and interactions. Therefore, it is inevitable to synthesize the peripheral bind motif and carefully tailor the variety and number of interaction sites on building blocks, thus bringing disadvantages such as poor tunability and hard extendibility.Multicompartment assemblies attract much attention for their wide applications. However, the fabrication of multicompartment assemblies usually requires elaborately designed building blocks and careful controlling. The emergence of droplet networks has provided a facile way to construct multiple droplet architectures, which can further be converted to multicompartment assemblies. Herein, the bind motif-free building blocks are presented, which consist of the hydrophobic Tf 2 N − -based ionic liquid (IL) dissolving LiTf 2 N salt, that can conjugate via arrested coalescence in confined-space templates to form IL droplet networks. Subsequent ultraviolent polymerization generates robust free-standing multicompartment assemblies. The conjugation of building blocks relies not on the peripheral bind motif but on the interfacial instability-induced arrested coalesc...