Using a combination of modeling and experiments, we show that miktoarm star macromolecules act as molecular/mechanical linkers in the fabrication of multilayer stackable gels, which are formed by sequential controlled radical polymerization of successive layers in incompatible solvents. Dissipative particle dynamics simulations indicate that miktoarm star copolymers localize at the interface between the incompatible solvents and act as molecular bridging agents between the respective gel layers. Miktoarm stars composed of poly (n-butyl acrylate)-co-poly ((oligo (ethylene glycol) methacrylate) were synthesized by atom transfer radical polymerization (ATRP) and successfully used as an interfacial compatibilizer/linker in mechanically interconnected bilayer stacks comprised of a primary layer of cross-linked hydrophobic n-butyl methacrylate polymerized in toluene and of a secondary layer of cross linked hydrophilic 2-(dimethylamino)ethyl methacrylate polymerized in water. Without the miktoarm stars, no connection between the two layers could be obtained. (C) 2016 Elsevier Ltd. All rights reserved.