In this study we demonstrate that different hierarchically self-assembled materials can be formed by recently developed ferritin-polymer hybrid conjugates. Via interfacial self-assembly in combination with small-pore extrusion followed by inter-particle UV cross-linking, different states of capsule structures were obtained ranging from single capsules to capsules entrapped in fibers and high density capsule assemblies. The release of the capsule contents is regulated using different solvent combinations and visualized by entrapment of a lipophilic molecular dye. The structures and release properties were investigated using (fluorescence) microscopy and UV-Vis spectroscopy. (C) 2012 Elsevier Ltd. All rights reserved.