Rigid crosslinked polyacrylamide monoliths with well-defined macropores have been successfully fabricated by organotellurium-mediated living radical polymerization (TERP) accompanied by spinodal decomposition. The TERP forms homogeneous networks derived from N,N-methylenebis(acrylamide) (BIS), in which spinodal decomposition is induced to form macropores. Macropore diameter can be controlled from submicrons to a few microns, and also the obtained networks contain mesopores in the macroporous skeletons, which are collapsed by evaporative drying. They are promising materials with hydrophilic polyacrylamide surfaces and have enough strength to preserve the macropores from the surface tension arising in the repetitive swelling and drying that may occur in many applications.