The synthesis of a series of poly(ethylene oxide)-b-polystyrene copolymers with different block lengths was performed by radical addition fragmentation chain transfer. These amphiphilic copolymers were tested as stabilizers for water-in-oil medium internal phase emulsion (MIPE) templating polymerization and the formation of polyMIPEs with controlled morphology. Aside from the structure of the emulsion stabilizer, several parameters susceptible to influence the size of the cavities and the interconnectivity of the porous monoliths were probed including the choice of the comonomers, treatment of the emulsion by ultrasound, the use of controlled radical polymerization method for the network formation as well as interfacial initiation. Interconnected cellular monoliths were produced. The polymerization of the ultrasonicated water-in-ethylhexylacrylate/divinylbenzene MIPE notably led to near-mesoporous open-cell material. Mechanical properties and specific surface areas of the polyMIPEs were also investigated and discussed. (C) 2016 Elsevier Ltd. All rights reserved.