We report the self‐assembly and characterization of mesoporous silica thin films with a 3D ordered arrangement of isolated spherical pores. The preparation method was based on solvent‐evaporation induced self‐assembly (EISA), with MTES (CH3–Si(OCH2CH3)3) as the silica precursor and a polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) diblock copolymer as the structure‐directing agent. The synthetic approach was designed to suppress the siloxane condensation rate of the siloxane network, allowing co‐self‐assembly of the silica and the amphiphile, followed by retraction of the PEO chains from the silica matrix and matrix consolidation, to occur unimpeded. The calcined films retained the methyl ligands and exhibited no measurable microporosity, thereby indicating that the 3D‐ordered spherical mesopores are not interconnected. A solvent‐mediated formation mechanism is proposed for the absence of microporosity. Due to their closed porosity and hydrophobicity, the MTES‐based films and MTES‐TEOS (Si(OCH2CH3)4)‐based hybrid films we describe should be promising for applications such as low‐k dielectrics.

Scalable synthesis of multicompartment polyion complex (PIC) systems has been achieved via visible light-initiated RAFT polymerization of cationic monomer in the presence of anionic diblock copolymer micelles in water at 25 °C. This polymerization-induced hierarchical electrostatic self-assembly (hierarchical PIESA) implements structural hierarchy via programmable self-assembly to form multicompartment PIC micelles and their monolayer colloidal nanosheets and nanocages. The anionic micelles play decisive roles in such a hierarchical PIESA to access biologically relevant yet otherwise inaccessible multicompartment PIC systems.

We present a template strategy for precision synthesis of “complex coacervates-in-dodecyl atmosphere” ultrathin lamellae possessing exceptional shape-preservation and charge-tolerance properties.

Macromolecular crowding plays a key role in liquid-phase condensation of proteins and membraneless organelles yet is largely unexplored for artificial liquid materials. Herein, we present a strategy for direct access to multiphase liquid condensates with individual charged/neutral subdomains, by introducing macromolecular crowding to our previous protocol of liquid–liquid phase-separation-driven polymerization-induced electrostatic self-assembly (LLPS-PIESA). We show that reversible addition fragmentation chain transfer (RAFT) aqueous dispersion photo-copolymerization of a charged monomer with a specific neutral monomer, in the presence of a polar macrochain transfer agent (CTA) and an oppositely charged polyion, can induce self-sorting and macromolecular crowding. LLPS-PIESA proceeds via liquid-phase condensation of as-assembled nascent clusters up to biologically important nanostructured multiphase condensates with individual charged/neutral subdomains.