Highly porous polymers (polyHIPEs) incorporating activated esters have been prepared by photopolymerisation of high internal phase emulsions (HIPEs) containing pentafluorophenyl acrylate (PFPA) in the monomer phase. The resulting materials have nominal porosity of 80% and a well-defined, interconnected pore morphology with average pore diameters ranging from 30 to 50 mu m. PFPA could be added at up to 50 wt% of the monomer phase without destabilising the HIPE noticeably, however analysis of the polyHIPE materials revealed that only around half of this was incorporated into the final porous materials. The pentafluorophenyl groups were shown to be reactive towards a range of amines (tris-(2-aminoethyl)amine, benzylamine and Rhodamine 123), giving near complete loss of fluorine over the period of the reaction. The extent of functionalisation was however determined to be around 50% by elemental analysis, suggesting some loss of fluorine by hydrolysis of activated esters. We believe that this represents a facile method for the preparation of a variety of well-defined functional porous polymers by a post-polymerisation functionalisation route. (C) 2013 Elsevier Ltd. All rights reserved.