Porous poly(ethylene glycol) diacrylate (PEGDA) monoliths have been prepared by UV-initiated polymerization of PEGDA oligomer (M-n = 700 g/mol). In the mean time, the addition of hydrophobic poly(propylene oxide) (PPO, M-n = 725 g/mol) as porogen into an ethanol solution of PEGDA oligomer to form a homogenous mixture, causes a phase separation between PPO and PEGDA following removal of ethanol by UV heating. Porous PEGDA monolith was prepared by immediate heating at 300 degrees C to remove PPO molecules from the as-synthesized PEGDA/PPO hybrid. The micrometer pores of the PEGDA monolith have relatively concentrated pore size distribution according to the mercury intrusion porosimetry results and field emission scanning electron microscopy (FE-SEM).