Stable w/o high internal phase emulsion (HIPE) using cetyltrimethylammonium bromide (CTAB) as the sole surfactant was prepared with long time further mixing of the emulsion after the addition of aqueous phase was completed, although it was generally considered the emulsion would be unstable according to Bancroft rule. The delta backscattering data of these emulsions showed that the further mixing enhanced the stability of the HIPE significantly, because a dram partial of monomers was initiated in the period of preparing the emulsion, which reduced the diffusion of CTAB from the on phase to aqueous phase and increased the viscosity of the continuous phase. In addition, the morphology of polyHIPEs based on this type HIPEs was tailored. Increasing aqueous phase fraction resulted in the increase of pore volume which could be up to 24.0 ml/g. Increasing the polymerization temperature led to an increase in average void and interconnect diameter in the resulting porous materials. Additionally, the presence of additives, PEG and ethanol, in the aqueous phase was found to increase the average void diameter remarkably. The interconnect diameter of the materials could be controlled at constant pore volume by tuning PEG and ethanol concentration in the aqueous phase. It was suggested that coalescence was the dominant effect in determining the morphology of the polyHIPEs prepared in the presence of PEG, and Ostwald ripening was the major role in tailoring the morphology of the porous materials with ethanol. (C) 2008 Elsevier Ltd. All rights reserved.