Poly(high internal phase emulsion) materials were prepared from concentrated emulsions containing 4-vinylbenzyl chloride as the reactive monomer and divinylbenzene as the cross-linker. Emulsions consisted of 80 vol. % aqueous phase (water, CaCl2, initiator) and 20 vol. % of organic phase (monomers, surfactant Span 80 and a porogenic solvent). Polymerized samples were purified and investigated for morphology and porosity by scanning electron microscopy, nitrogen adsorption/ desorption and inverse steric exclusion chromatography (ISEC). It was found that no substantial additional dry porosity was achieved by the addition of solvents (as determined by nitrogen adsorption) while wet microporosity was substantially improved as determined by the ISEC method. The process of drying the polyHIPE materials also influenced the wet porosity.