Using styrene, divinylbenzene as comonomers, ammonium persulfate as initiator, hexadecyltrimethylammonium bromide as emulsifier, porous polystyrene/ divinylbenzene (PSD) was synthesized by high internal phase emulsions (HIPEs) as template. The effects of ethanol volume fraction (relative to dispersed phase) on the emulsion stability and the properties of the PSD，such as density, absorption (release) effects of liquid, and swelling ratio, were investigated. It was more difficult to form a stable emulsion with the increase of alcohol content. In addition, the density, absorption of the liquid, swelling ratio of the PSD decreased, the release of toluene increased with the increasing of alcohol. It is worth mentioning that, after the PSDs were extracted by water-ethanol, the absorption rate of water decreased to 0.26 cm3/g, while the absorption rate of toluene was still 15.60~18.42 cm3/g. Thus, we would obtain a hydrophobic and lipophilic resin from this way.