Rigid methacrylate-based polymer monoliths with well-defined macropores have been synthesized from glycerol 1,3-dimethacrylate (GDMA) and trimethylolpropane trimethacrylate (Trim) by organotellurium-mediated living radical polymerization. In each system, poly(ethylene oxide) induced spinodal decomposition with the progress of polymerization of COMA or Trim. Well-defined macroporous structure can be tailored by fixing the bicontinuous structure by the sol gel transition. Both polymer monoliths possessed macropores with narrow size distributions and the macropore size can be controlled simply by varying the amount of poly(ethylene oxide). Starting from GDMA, polymer monoliths with unimodal macropores can be obtained due to the collapse of micro- and mesopores, which were originally embedded in macropore skeletons, by large shrinkage during drying. In contrast, starting from Trim, the obtained polymer monoliths include not only macropores but also micro- and mesopores, which lead to high specific surface area (470 m(2) g(-1)), owing to the higher crosslinking density. (C) 2011 Elsevier Ltd. All rights reserved.