Microfluidic devices allow preparation of water-in-oil-in-water (W/O/W) double emulsions with defined droplet sizes. In these double emulsions, an oil layer separates a water-filled compartment from the surrounding bulk water. If the oil layer contains compounds that can cure and solidify, the double emulsion droplet can be converted into a microcapsule in which a thin shell surrounds a liquid aqueous interior. These microcapsules are useful for several applications, including drug or fragrance delivery, cosmetics and food additives encapsulation, as microreactors for enzymes, or as a shell for artificial cells. Double emulsion capsules have also been used to encapsulate nanoparticles, for instance, TiO2 and ZnO nanoparticles, to create catalytic systems that can degrade organic pollutants. Shell materials of these microcapsules can be synthetic or natural polymers, or colloidal particles that stabilize the oil phase. These components or their precursors must be soluble in the oil phase, namely an organic solvent that is not miscible with water. Thus, they are usually hydrophobic polymers, hydrophobic monomers, hydrophobic colloidal particles, or mixtures thereof. As a result, double emulsion microcapsule walls are also hydrophobic and, therefore, impermeable for water or watersoluble compounds, unless the capsule wall is micro-or nanoporous. However, a shell that is semipermeable for water-soluble compounds is essential for many applications. These include, for example, applications requiring slow release of hydrophilic cargo from the inside of the capsules, or the transport of water-soluble substrates to reach the catalysts within capsule microreactors. One possibility to create more polar shells is to use polymers that are soluble in water and in organic solvents, such as poly(ethylene glycol) (PEG). Indeed, hydrogel microcapsules could be prepared by polymerization of PEG macrocrosslinkers, such as α,ωdimethacrylate-terminated PEG. However, when dried, PEG hydrogels lose their elasticity and, therefore, it is difficult to dry such hydrogel microcapsules without damaging the capsules. Other approaches to create double emulsion microcapsules that allow for transport of hydrophilic compounds across their shell have been proposed. For example, capsules with a permeable self-healing shell have been prepared using a dynamically-crosslinked polymer network that can seal holes formed upon capsule cracking. In other instances, permeable capsules have been made through phase separation of polymers during UV-induced polymerization of the middle oil fluid, or by packing colloids in the middle phase to form colloidosomes with intrinsically microporous shells. However, such microcapsules usually lack mechanical stability and toughness, and may show limited functionalization capability. Amphiphilic polymer conetworks (APCNs) can potentially address several of the drawbacks of currently available shell materials. APCNs are composed of chemically crosslinked hydrophilic and hydrophobic polymer chain segments, and are exquisite materials with unique properties. They are hydrogels that also swell in organic solvents. As the covalent crosslinks hinder macroscopic demixing of the chain segments of opposite polarity (i.e. macroscopic spinodal phase separation), APCNs possess nanophase-separated morphologies that are often co-continuous over a broad range of compositions, thereby allowing for diffusion of dissolved molecules across the material. This makes them semipermeable and suitable for membrane and drug-delivery applications. Moreover, they are transparent, biocompatible, and possess good mechanical properties, including elasticity when swollen and when dry, lending themselves mechanically superior to other hydrogels.