The purpose of this research was to synthesize the new type of adsorbent for CO2 adsorption. The polymer obtained from high internal phase emulsion or “polyHIPE” can be polymerized from divinylbenzene (DVB) and vinyl benzyl chloride (VBC). Polyethyleneimine (PEI) was added into the polyHIPE during polymerization reaction to increase the CO2 capture efficiency. For the effect of the monomer ratio (DVB/VBC), the polyHIPE for every ratio has the same appearances which are white, brittle and chalky porous solid. The surface area of the polyHIPE increased when the amount of DVB was increased. The highest surface area was found in the monomer ratio of 100/0 or 100 % DVB,which was 303.0 m2/g. When 10 wt% PEI was added into the polyHIPE, the percentage of PEI loading was very low at 100/0 monomer ratio; there was only 0.11 wt% of PEI. As the ratio of VBC increased from 10 % to 50 %, the percentage of PEI loading in the polyHIPE was increase up to 1.7 wt% and then stayed almost constant because 10 wt% PEI can react completely with 1.26% VBC. Moreover, when the percentage of PEI in the prepared solution was increase, the percentage of PEI in polyHIPE was also increase, and the highest percentage of PEI in polyHIPE was 2.57 wt%.