Macroporous poly(acrylamide) hydrogels have been synthesized by using poly(ethylene glycol) (PEG) with three different molecular weights as the pore-forming agent. Scanning electron microscope graphs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights of PEG during the polymerization reaction. The swelling ratios of the PEG-modified hydrogels were much higher than those for the same type of hydrogel prepared via conventional method. However, the swelling/deswelling ratios of the PEG-modified hydrogels were affected slightly by the change in the amount of the PEG. Scanning electron microscopy experiments, together with swelling ratio studies, reveal that the PEG-modified hydrogels are characterized by an open structure with more pores and higher swelling ratio, but lower mechanical strength, compared the conventional hydrogel. PAAm has potential applications in controlled release of macromolecular active agents.