Mechanically robust microcapsules with water-swellable and semi-permeable shells can be prepared by microfluidic double emulsification using PHEA-l-PDMS APCNs as wall materials. By polymerizing a hydrophobically masked monomer with a PDMS-based macromolecular crosslinker, it became possible to create silicon hydrogels that are templated by the oil phase of the double emulsion, and therefore form the shell of the microcapsules. These APCNs greatly expand the material scope of double emulsion microcapsules. For example, the APCN microcapsules can be dried and rehydrated multiple times without damage. They are semipermeable for water and small water-soluble compounds while retaining macromolecules in their inside. Moreover, they can host catalytically active nanoparticles and thereby serve as microreactors or be selectively modified with a suitable linker on their surface. Thus, APCN microcapsules should be useful for a variety of applications that involve encapsulation and controlled release of active compounds such as drugs or fragrances. Alternatively, they could be used as catalytically active building blocks for molecular systems engineering or as compartments for the preparation of artificial cells. Furthermore, APCNs are transparent, so that the capsules could also be used as adaptable optical materials such as microlenses.