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The formation of the interconnected morphology of open-cell styrene/divinylbenzene (DVB) PolyHIPE copolymers has been studied by scanning electron microscopy on frozen HIPE samples at different stages of polymerisation, a technique known as cryo-SEM. The transition from discrete emulsion droplets to interconnected cells was observed to occur around the gelpoint of the polymerising system. This would suggest that the formation of holes between adjacent cells is due to the contraction of the thin monomeric films on conversion of monomer to polymer, as a result of the higher density of the latter.