Highly porous and interconnected methacrylate-based porous materials were prepared by photopolymerisation of the continuous phase of high internal phase emulsion (HIPE) templates. The rapid cure afforded by photopolymerisation effectively 'locks' the emulsion morphology prior to emulsion destabilisation, in comparison to thermally-initiated HIPEs of similar compositions. Contrary to expectation, it was observed that fully cured photopolymerised polyHIPEs could be prepared with a thickness of up to 35 mm, despite the severe opacity of the parent emulsions. This is attributed to a photofrontal polymerisation process, where radicals generated on the surface propagate rapidly through the bulk of the emulsion. Homogeneous, well-defined polyHIPE materials of up to 95% nominal porosity were obtained by photopolymerisation of HIPEs containing up to 30 vol.% glycidyl methacrylate (GMA) in the monomer phase (the remaining monomers and crosslinker are acrylates). Surprisingly, poly(ethylene glycol) methacrylate (PEG-MA), a nonionic monomer that is miscible with both emulsion phases, could be added to such HIPEs after preparation. On polymerisation, hydrophilic, water-wettable porous materials were obtained. Finally, it was also demonstrated that all-methacrylate HIPEs could be prepared and cured to yield GMA-containing polyHIPEs. These findings demonstrate the versatility of photopolymerisation for the preparation of emulsion templated porous polymers. (c) 2012 Elsevier Ltd. All rights reserved.