Abstract: Methods of synthesizing multilayer structures, including multilayer capsules, tubes and hair-covered substrates, are provided. A substrate is provided comprising a polymerization initiator. The initiator-loaded substrate is exposed to a solution comprising a monomer and crosslinker. The initiator diffuses outwardly from the substrate, thereby initiating polymerization of the monomer and forming a layered structure comprising a polymer portion disposed on an exterior surface of the substrate. The process may be repeated for a selected number of cycles, thereby forming a multilayer structure having a selected number of layers. The composition, thickness and properties of each layer are selectively controlled. Multilayer structures formed in accordance with the methodologies are also provided.