An experimental study on the preparation of monolithic porous polymers by environmentally friend process in supercritical carbon dioxide has been carried out. Polymerization mixture composed of a cross-linking monomer, initiator and functional co-polymer was charged in the reactor with sapphire window. After the system was purged with a flow of CO2 for 15 min, the reactor was pressurized with liquid CO2 up to 100 bars. The reactor was isolated from and placed back to the system via quick connector for shaking until the mixture had become fully homogeneous. The reactor was then heated and pressurized to the required reaction conditions and left overnight. After cooling and CO2 evacuation, the polymer was removed from the reactor as dry, white, continuous monoliths. The effect of experimental conditions on the physical properties of porous polymer was systematically examined, and it was found that monomer content had a major effect on the physical properties of the polymers.