Hydrophilic surface modification of porous epoxy monoliths was carried out by introducing the initiator into the wall of pores and then polymerizing acrylic acid monomer onto the surface. The porous epoxy monolith was prepared via concentrated emulsion polymerization template. Before fully curing of epoxy, the free radical initiator was immobilized on the pore surface by swelling the porous epoxy monolith in initiator/acetone solution. After acrylic acid monomers were infiltrated into the pores and then polymerized, the hydrophilic polymer layers were generated on the wall of pores. The effects of the curing time of epoxy and the swelling time in solution on the morphology of poly (acrylic acid) layers were discussed. The polymerization of hydrophilic polymer on the pore surface of the porous monolith was investigated by scanning electron microscopy, transmission electron microscopy, and energy-dispersive spectrometer. The hydrophilic modification and the wettability of the surface of pores in porous epoxy monoliths were studied by water contact angle and water absorption measurement.