In recent years, open porous materials (polyHIPEs) have attracted more and more attention because of their specific properties and applications in biological tissue scaffolds, catalysis supports and ion-exchange resin. However, the surfactants used in this type material were limited to nonionic surfactants or the mix of nonionic surfactant and ionic surfactant. In this work, firstly well-defined polyHIPEs were synthesized by W/O emulsions with ionic surfactant alone (e.g., CTAB). Furthermore, the polyHIPEs with much higher pore volume (14.7 cm(3) g(-1)), uniform pore diameter and cell size were obtained by this method. Both the median pore diameter and average cell size of the polyHIPEs rose with increase of DVB concentration and/or water fraction. (C) 2007 Elsevier Ltd. All rights reserved.